Behavior of Samarium III during the sorption process

International Nuclear Information System (INIS)

Ordonez R, E.; Garcia G, N.; Garcia R, G.

2004-01-01

In this work the results of the behavior of samarium in solution are presented, in front of a fine powder of zirconium silicate (zircon). For that which is necessary to characterize the zircon, studying the crystallinity, the morphology, the surface area and the isoelectric point. The behavior of samarium in solution is studied by means of the elaboration of isotherm of sorption, using the technique by lots. One observes that to pH values of nearer to the isoelectric point (pH = 7.23) the process of sorption of the samarium begins, reaching a maximum to near pH at 9. The technique of luminescence is used to determine the concentration of the sipped samarium (phosphorescence) and also to make the speciation of the species formed in the surface of the zircon (phosphorescence). The results can be extrapolated with the plutonium when making the modeling of the migration of alpha emitting coming from the repositories of radioactive waste since both they have similar chemical properties (they are homologous). (Author)

The ion-exchange obtaining of high purity samarium oxide

International Nuclear Information System (INIS)

Brzyska, W.; Soltysiak, I.; Cygan, J.

1987-01-01

The use of lactic acid - EDTA mixture as an eluent for the obtaining of high purity samarium oxide was studied. The studies were carried out at room temperature on cation exchange resin Wofatit KPS X 8. The best results were obtained for lactic acid (0,26 mol/dm 3 ) - EDTA (0,013 mol/dm 3 ) mixture at pH 3,3. As the result of 57% samarium concentrate elution with column load 1:3 and flow rate 0,4 cm/min, over 99% pure samarium oxide with 73% yield has been obtained. The yield of spectrally pure Sm 2 O 3 exceeded 45%. (author)

Implementation of an analytical technique for Samarium; Implementacion de una tecnica analitica para Samario

Energy Technology Data Exchange (ETDEWEB)

Garcia G, N. [ININ, Carretera Mexico-Toluca Km. 36.5, 52045 Estado de Mexico (Mexico)

2004-07-01

Since the Samarium presents the same chemical properties that the plutonium, it has been used as homologous in studies that allow us to know the behavior that the plutonium presents in solution, with the advantage of working with an inactive and not very dangerous element. At the moment studies of sorption of plutonium or samarium are made on some mineral matrices that present certain surface properties. Due to the low concentrations that are used in the studies of sorption of samarium on those reagent substrates, their detection becomes very difficult for the conventional analysis media. The luminescence is a technique that can detect lower concentrations, smaller at 1 X 10{sup -} {sup 2} M, but when fluorofors are used this limit of detection increases in several orders of magnitude. In this work it has been used the arsenazo-III as fluorofor agent since it reacts in a specific way with the samarium, forming a complex that presents a proportional luminescence to the concentration of the present samarium. The advantage of making the quantification of samarium by luminescence is that it can use the same instrumental equipment to determine the speciation of the samarium sipped in the zircon. (Author)

Polypyrrole-coated samarium oxide nanobelts: fabrication, characterization, and application in supercapacitors

Science.gov (United States)

Liu, Peng; Wang, Yunjiao; Wang, Xue; Yang, Chao; Yi, Yanfeng

2012-11-01

Polypyrrole-coated samarium oxide nanobelts were synthesized by the in situ chemical oxidative surface polymerization technique based on the self-assembly of pyrrole on the surface of the amine-functionalized Sm2O3 nanobelts. The morphologies of the polypyrrole/samarium oxide (PPy/Sm2O3) nanocomposites were characterized using transmission electron microscope. The UV-vis absorbance of these samples was also investigated, and the remarkable enhancement was clearly observed. The electrochemical behaviors of the PPy/Sm2O3 composites were investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge. The results indicated that the PPy/Sm2O3 composite electrode was fully reversible and achieved a very fast Faradaic reaction. After being corrected into the weight percentage of the PPy/Sm2O3 composite at a current density of 20 mA cm-2 in a 1.0 M NaNO3 electrolyte solution, a maximum discharge capacity of 771 F g-1 was achieved in a half-cell setup configuration for the PPy/Sm2O3 composites electrode with the potential application to electrode materials for electrochemical capacitors.

Separation of lanthanum (3) and samarium (3) extraction with tributylphosphate in the solvent presence of solid phase

International Nuclear Information System (INIS)

Korotkevich, I.B.; Kolesnikov, A.A.; Bomshtejn, V.E.

1990-01-01

Lanthanum (3) and samarium (3) extraction from nitric acid solutions by tributylphosphate in the presence of solid phase has been investigated. An increase in samarium α-nitrate distribution factor in the presence of solid phase with a decrease in its concentration in the initial solution and with lanthanum nitrate concentration increase is detected. The greatest effect of separation is observed in samarium nitrate microregion. The method of quantitative extraction of samarium from lanthanum nitrate solutions with samarium-lanthanum separation factor exceeding 50 has been suggested

Synthesis of samarium complexes with the derivative binder of Schiff Quinolinic base. Characterization and photophysical study

International Nuclear Information System (INIS)

Lucas H, J.

2016-01-01

In this work we determined the metal: binder stoichiometry of the species formed during the UV/Vis spectrophotometric titration of the derivative binder of Schiff quinolinic base, L1 with the samarium nitrate pentahydrate in methanol. Statistical analysis of the data allowed proposing the metal: binder stoichiometry for the synthesis of the complexes which was one mole of samarium salt by 2.5 moles of binder and thus favor the formation of complexes with 1M: 1L and 1M: 2L stoichiometries. They were synthesized in aqueous-organic medium (water-ethanol), isolated and purified two complexes with stoichiometry 1 Sm: 1 L1, complex 1 and 1 Sm: 2 L1, complex 2. The overall yield of the reaction was 76%. The characterization of the formed complexes was performed by visible ultraviolet spectrometry (UV/Vis), nuclear magnetic resonance, X-ray photoelectron spectroscopy (XP S), thermal gravimetric analysis with differential scanning calorimetry (TGA/DSC), and radial distribution function. These complexes were studied by fluorescence and emission phosphorescence at variable temperature. Spectroscopic techniques used in both solution and solid demonstrated the formation and stability of these complexes. In addition XP S indicated that in both complexes the samarium retains its oxidation state 3+. Luminescence studies indicated that there is intra-binding charge transfer which decreases the transfer of light energy from the binder to the samarium. Based on the experimental results, L1 binder molecules and complexes 1 and 2 were modeled that demonstrated the proposed Nc for each complex, as well as allowed to visualize the structural arrangement of the molecules, complexes and binder. (Author)

Biodistribution study of 153Sm-EDTMP produced by irradiation of natural and enriched Samarium, in rats

International Nuclear Information System (INIS)

Meftahi, M.; Bahrami Samani, A.; Babaei, M. H.; Shamsaei Zafarghandi, M.; Ghannadi Maragheh, M.

2010-01-01

''1 53 Sm-EDTMP is one of the well known radiopharmaceuticals for pain palliation of bone metastases. Despite that, it is used just in a few countries. It is due to some reasons like being costly enriched samarium that usually used as target for irradiation and short half-life of 153 Sm. In this investigation, certain amounts of radiopharmaceuticals prepared by irradiation of enriched and natural samarium were injected to some normal rats. Then, the rodents were sacrificed and some of their organs were removed. All of the mentioned stages were performed in order to consider the possibility of exploiting natural samarium instead of enriched samarium by study of biodistribution of both radiopharmaceuticals in various organs especially in bone as the target tissue. At the end, the acceptable results were obtained using natural samarium in comparison with the enriched samarium from the point of view of the biodistribution studies.

Influence of tellurite on lifetime for samarium doped lanthanum lead borate glass

Science.gov (United States)

Madhu, A.; Eraiah, B.

2018-04-01

Samarium substituted tellurium lanthanum lead borate glass is prepared using melt quenching technique. Luminescence spectra have been recorded upon excitation with 402 nm various transitions from 4G5/2 level, for samarium doped tellurite glasses are studied and also lifetime for all the samples exhibit single exponential behaviour of decay curve. Luminescence spectra of present glasses show quenching effect due to cross-relation channels of samarium ions. The lifetime of glass samples decrease as the tellurite concentration is decreased. So, it evidences that to attain longer lifetime for lasing material one can tune the host by selecting concentration of tellurite.

A NOVEL SAMARIUM COMPLEX WITH INTERESTING ...

African Journals Online (AJOL)

delocalized π-electrons of the pyridyl rings obtains increasing attention in ... BaSO4 plate was used as a reference (100% reflectance), on which the finely ground .... several are samarium-containing complex with bipy [41-45]. Figure 2.

Solubility isotherms in ternary systems of samarium nitrate, water and nitrates of amidopyrine, benzotriazole

International Nuclear Information System (INIS)

Starikova, L.I.

1991-01-01

Solubility in the system of samarium nitrate-amidopyrine nitrate-water at 25 and 50 deg C was studied. Solubility isotherms consist of three branches, corresponding to crystallization of samarium nitrate tetrahydrate, amidopyrine nitrate and congruently soluble compounds of Sm(NO 3 ) 3 · 2C 13 H 17 ON 3 ·HNO 3 composition. Its thermal behaviour was studied. The system of samarium nitrate-benzotriazole nitrate-water is referred to eutonic type

Polypyrrole-coated samarium oxide nanobelts: fabrication, characterization, and application in supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Liu Peng, E-mail: pliu@lzu.edu.cn; Wang Yunjiao; Wang Xue; Yang Chao; Yi Yanfeng [College of Chemistry and Chemical Engineering, Lanzhou University, Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu Province and State Key Laboratory of Applied Organic Chemistry (China)

2012-11-15

Polypyrrole-coated samarium oxide nanobelts were synthesized by the in situ chemical oxidative surface polymerization technique based on the self-assembly of pyrrole on the surface of the amine-functionalized Sm{sub 2}O{sub 3} nanobelts. The morphologies of the polypyrrole/samarium oxide (PPy/Sm{sub 2}O{sub 3}) nanocomposites were characterized using transmission electron microscope. The UV-vis absorbance of these samples was also investigated, and the remarkable enhancement was clearly observed. The electrochemical behaviors of the PPy/Sm{sub 2}O{sub 3} composites were investigated by cyclic voltammetry, electrochemical impedance spectroscopy, and galvanostatic charge-discharge. The results indicated that the PPy/Sm{sub 2}O{sub 3} composite electrode was fully reversible and achieved a very fast Faradaic reaction. After being corrected into the weight percentage of the PPy/Sm{sub 2}O{sub 3} composite at a current density of 20 mA cm{sup -2} in a 1.0 M NaNO{sub 3} electrolyte solution, a maximum discharge capacity of 771 F g{sup -1} was achieved in a half-cell setup configuration for the PPy/Sm{sub 2}O{sub 3} composites electrode with the potential application to electrode materials for electrochemical capacitors.

Basis for developing samarium AMS for fuel cycle analysis

International Nuclear Information System (INIS)

Buchholz, Bruce A.; Biegalski, Steven R.; Whitney, Scott M.; Tumey, Scott J.; Jordan Weaver, C.

2010-01-01

Modeling of nuclear reactor fuel burnup indicates that the production of samarium isotopes can vary significantly with reactor type and fuel cycle. The isotopic concentrations of 146 Sm, 149 Sm, and 151 Sm are potential signatures of fuel reprocessing, if analytical techniques can overcome the inherent challenges of lanthanide chemistry, isobaric interferences, and mass/charge interferences. We review the current limitations in measurement of the target samarium isotopes and describe potential approaches for developing Sm-AMS. AMS sample form and preparation chemistry will be discussed as well as possible spectrometer operating conditions.

4f and 5d magnetism in samarium

International Nuclear Information System (INIS)

Stunault, A.; Bernhoeft, N.; Vettier, C.; Dumesnil, K.; Dufour, C.

2001-01-01

We report on resonant magnetic X-ray scattering studies of a samarium epitaxial film at the samarium L 3 edge. We observe one quadrupolar resonance below the edge, reflecting the polarization of the 4f electrons, and two dipolar resonances above the edge, related to the polarization of the 5d band. We demonstrate, by following the thermal evolution of resonant magnetic intensities of both types, that the polarization of the 4f and 5d electrons present exactly the same temperature dependence, even very close to the ordering temperature, in agreement with the RKKY model for long-range magnetic order in rare earths

Studies on ultrasonic velocity and electrical conductivity of samarium soaps in non-aqueous medium

International Nuclear Information System (INIS)

Mehrotra, K.N.; Chauhan, M.; Shukla, R.K.

1990-01-01

The ultrasonic velocity of solutions of samarium soaps in non-aqueous medium has been measured at a constant temperature and the results have been used to evaluate the various acoustic parameters. The pre-micellar association and the formation of micelles in samarium soap solutions have been determined by conductometric measurements. The molar conductance at infinite dilution, degree of ionisation and ionisation constant have been evaluated. The results show that samarium soaps behave as weak electrolyte in dilute solutions. (Authors)

Synthesis and application of a new fluorous-tagged ammonia equivalent

DEFF Research Database (Denmark)

Nielsen, Simon Dalsgaard; Smith, Garrick; Begtrup, Mikael

2010-01-01

A novel fluorous-tagged ammonia equivalent has been developed. It is based on a nitrogen-oxygen bond, which can be cleaved in a traceless manner by a molybdenum complex or samarium diiodide. The application in the synthesis of ureas, amides, sulfonamides, and carbamates is described. The scope of...... of the fluorous N--O linker is exemplified by the synthesis of itopride, a drug used for the treatment of functional dyspepsia. Itopride was synthesized with the aid of fluorous purification methods and the product was isolated in good overall yield, with high purity....

Diffusion of samarium into cobalt in the reduction-diffusion process

International Nuclear Information System (INIS)

Freitas Nogueira, P. de; Neto, F.B.; Landgraf, F.J.G.

1998-01-01

The presence of metallic cobalt in samarium-cobalt powders is a major cause for low magnetic properties in magnets. This paper intends to investigate the effect of time and temperature in the microstructure of powders produced by reduction-diffusion. This process, developed for the production of rare earth-transition metal alloys, consists on the reduction of the rare earth oxide with metallic calcium (or calcium hydride) and its subsequent diffusion into the cobalt particle. In the present work, a mixture of samarium oxide, cobalt powder and metallic calcium was heated to 1100 or 1200 C for 2 or 4 hours in a tubular furnace under one atmosphere of purified argon. The material thereof obtained, a sintered mass is disintegrated by aqueous crepitation. The powder was evaluated in terms of its chemical composition, its samarium yield and the intermetallic compounds present. The samarium, oxygen and calcium content of the powders produced were adequate for magnet production. However, despite the massive formation of the SmCo 5 compound after 2 hours at 1100 C, final homogeneity is attained only after 4 hours at 1200 C, with the presence of SmCo 5 and Sm 2 Co 7 and the absence of the Sm 5 Co 19 compound. Also, metallic cobalt and Sm 2 Co 17 were observed in the materials produced after 2 hours at 1100 or 1200 C. (orig.)

Nonlinear Faraday rotation in samarium vapor

International Nuclear Information System (INIS)

Barkov, L.M.; Melik-Pashaev, D.A.; Zolotorev, M.S.

1988-01-01

Experiments on nonlinear magnetic optical (Faraday) rotation on resonance transitions of atomic samarium are described. Measurements were carried out on transitions with different angular momenta of upper and lower states: 1→0, 0→1 and 1→1. Qualitative explanations of observed phenomena are given

Plasma sprayed samarium--cobalt permanent magnets

International Nuclear Information System (INIS)

Willson, M.C.; Janowiecki, R.J.

1975-01-01

Samarium--Co permanent magnets were fabricated by arc plasma spraying. This process involves the injection of relatively coarse powder particles into a high temperature gas for melting and spraying onto a substrate. The technique is being investigated as an economical method for fabricating Co--rare earth magnets for advanced traveling wave tubes and cross-field amplifiers. Plasma spraying permits deposition of material at high rates over large areas with optional direct bonding to the substrate, and offers the ability to fabricate magnets in a variety of shapes and sizes. Isotropic magnets were produced with high coercivity and good reproducibility in magnetic properties. Post-spray thermal treatments were used to enhance the magnetic properties of sprayed deposits. Samarium--Co magnets, sprayed from Sm-rich powder and subjected to post-spray heat treatment, displayed energy products in excess of 9 million G-Oe and coercive forces of approximately 6000 Oe. Bar magnet arrays were constructed by depositing magnets on ceramic substrates

Spectroscopic Diagnostics of Barrier Discharge Plasmas in Mixtures of Zinc Diiodide with Inert Gases

International Nuclear Information System (INIS)

Guivan, N.N.; Malinin, A.N.

2005-01-01

The spectral characteristics of the emission of gas discharge atmospheric pressure plasmas in mixtures of zinc diiodide vapor with inert gases (He, Ne, Ar, Kr, and Xe) are investigated. The formation of a gas discharge plasma and the excitation of the components of a working mixture were performed in a high-frequency (with a repetition frequency of sinusoidal voltage pulses of 100 kHz) barrier discharge. The gas discharge emission was analyzed in the spectral range 200-900 nm with a resolution of 0.05 nm. Emission bands of ZnI(B-X) exciplex molecules and I* 2 excimer molecules, lines of inert gases, and emission bands of XeI* exciplex molecules (in Xe-containing mixtures) were revealed. It is ascertained that the strongest emission of ZnI* molecules is observed in ZnI 2 /He(Ne) mixtures. The regularities in the spectral characteristics of the gas discharge plasma emission are considered

Ferrites Ni0,5Zn0,5Fe2O4 doped with samarium: structural analysis, morphological and electromagnetic

International Nuclear Information System (INIS)

Costa, A.C.F.M.; Diniz, A.P.; Viana, K.M.S.; Cornejo, D.R.; Kiminami, R.H.G.A.

2010-01-01

This paper proposes to investigate the sintering at 1200 deg C/2h of Ni 0.5 Zn 0.5 Fe 2-x Sm x O 4 ferrite doped with 0.05; 0.075 e 0.1 mol of Sm synthesized by combustion reaction to evaluate the performance materials as absorbers of electromagnetic radiation. The influence of the concentration of samarium on the structure, morphology and electromagnetic properties of ferrites was studied. The resulting samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), magnetic measurements and reflectivity measurements in the frequency range between 8-12 GHz. The results showed that increasing the concentration of samarium caused a decrease in particle size of the samples, encouraging, therefore, to obtain materials with better values of magnetization and reflectivity, allowing for use as absorbers in narrow-band frequency between 9-10 GHz. (author)

Magnetoresistance of samarium in the 4.2-300 K range

International Nuclear Information System (INIS)

Trubitsyn, V.A.; Shalashov, V.F.

1980-01-01

Electric conductivity, transverse and longitudinal magnetoresistance of polycrystalline samarium with the purity of 99.9% in the 4.2-300 K temperature range and in magnetic fields up to 50 ke, are measured. The constituent of specific electric conductivity caused by spin disorder is 30.7 μOhmxcm, m*/m=2.6, the exchange parameter is G=3.1 eVxA 3 . Both transverse and longitudinal magnetoresistance are positive at 4.2 K; and the increase of temperature reveals a number of anomalies, evidently conditioned by the alteration of samarium magnetic structure

Cross sections for d-{sup 3}H neutron interactions with samarium isotopes

Energy Technology Data Exchange (ETDEWEB)

Luo, Junhua; He, Long [Hexi Univ., Zhangye (China). School of Physics and Electromechanical Engineering; Wu, Chunlei; Jiang, Li [Chinese Academy of Engineering Physics, Mianyang (China). Inst. of Nuclear Physics and Chemistry

2016-11-01

The cross sections for (n,x) reactions on samarium isotopes were measured at (d-T) neutron energies of 13.5 and 14.8 MeV with the activation technique. Samples were activated along with Nb and Al monitor foils to determine the incident neutron flux. Theoretical calculations of excitation functions were performed using the nuclear model codes TALYS-1.6 and EMPIRE-3.2 Malta with default parameters, at neutron energies varying from the reaction threshold to 20 MeV. The results were discussed and compared with experimental data found in the literature. At neutron energies 13.5 and 14.8 MeV, the cross sections of the {sup 149}Sm(n,p){sup 149}Pm reaction are reported for the first time. The cross sections of the {sup 150}Sm(n,p){sup 150}Pm, {sup 144}Sm(n,p){sup 144}Pm, {sup 152}Sm(n,α){sup 149}Nd and {sup 144}Sm(n,α){sup 141}Nd reactions at different neutron energies reported in the present work can be added as new data in the nuclear databases.

Conductometric investigations on samarium soaps

International Nuclear Information System (INIS)

Mehrotra, K.N.; Chauhan, Mithlesh; Shukla, R.K.

1989-01-01

The critical micelle concentration (CMC), degree of dissociation and dissociation constant of samarium soaps (valerate, caproate, caprylate and caprate) in a mixture of 60 per cent benzene and 40 per cent methanol were determined by using conductometric measurements. The soaps behaved as simple electrolyte in dilute solutions and the CMC was found to decrease with increasing chainlength of the fatty acid constituent of the soap. (author). 7 refs., 2 tabs

Optical isotope shifts for unstable samarium isotopes

International Nuclear Information System (INIS)

Eastham, D.A.; Walker, P.M.; Griffith, J.A.R.; Evans, D.E.; Grant, I.S.; England, J.G.; Fawcett, M.J.

1984-01-01

Using a tunable dye laser beam intersecting a thermal atomic beam, optical isotope shifts and hyperfine splittings have been measured for the four unstable samarium isotopes between 144 Sm and 154 Sm, covering the well known transition region from spherical to deformed shapes. (orig.)

Potentiometric study of samarium oxides formation from its chloride in a molten eutectic mixture of sodium and cesium chlorides

International Nuclear Information System (INIS)

Smolenskij, V.V.; Bove, A.L.; Del'mukhamedov, R.D.; Borodina, N.P.; Gavrilov, A.G.

1997-01-01

Interaction of trivalent samarium cations with oxide-ions in NaCl-2CsCl melt at 973 K has been studied by potentiometric method using electrochemical cell with two platinum-oxygen electrodes with a solid electrolyte membrane. The mechanism of the interaction and composition of the reaction products, depending on the medium oxyacidity, have been considered. Certain thermodynamic characteristics of the process have been calculated

Synthesis and application of a new fluorous-tagged ammonia equivalent.

Science.gov (United States)

Nielsen, Simon D; Smith, Garrick; Begtrup, Mikael; Kristensen, Jesper L

2010-04-19

A novel fluorous-tagged ammonia equivalent has been developed. It is based on a nitrogen-oxygen bond, which can be cleaved in a traceless manner by a molybdenum complex or samarium diiodide. The application in the synthesis of ureas, amides, sulfonamides, and carbamates is described. The scope of the fluorous N-O linker is exemplified by the synthesis of itopride, a drug used for the treatment of functional dyspepsia. Itopride was synthesized with the aid of fluorous purification methods and the product was isolated in good overall yield, with high purity. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fluorimetric determination of samarium(III) and europium(III) in neodymium oxide by separation with a resin column

Energy Technology Data Exchange (ETDEWEB)

Shaorong Liu; Jian Meng (Beijing Research Institute of Chemical Engineering and Metallurgy (China)); Wenhua Liu (General Research Institute for Non-Ferrous Metals (China))

1992-08-24

When thenoyltrifluoroacetone-phenanthroline-Triton X-100 is used to determine samarium(III) and europium(III) fluorimetrically, only a limited amount of neodymium(III) can be tolerated. By using an on- line separation which can partially separate neodymium(III) from samarium(III), a practical and convenient method was developed to detect samarium(III) at concentrations >0.05% and europium(III) at concentrations >0.005% in neodymium oxide. (author). 7 refs.; 4 figs.; 3 tabs.

Fluorimetric determination of samarium(III) and europium(III) in neodymium oxide by separation with a resin column

International Nuclear Information System (INIS)

Shaorong Liu; Jian Meng; Wenhua Liu

1992-01-01

When thenoyltrifluoroacetone-phenanthroline-Triton X-100 is used to determine samarium(III) and europium(III) fluorimetrically, only a limited amount of neodymium(III) can be tolerated. By using an on- line separation which can partially separate neodymium(III) from samarium(III), a practical and convenient method was developed to detect samarium(III) at concentrations >0.05% and europium(III) at concentrations >0.005% in neodymium oxide. (author). 7 refs.; 4 figs.; 3 tabs

Electrochemical extraction of samarium from molten chlorides in pyrochemical processes

International Nuclear Information System (INIS)

Castrillejo, Y.; Fernandez, P.; Medina, J.; Hernandez, P.; Barrado, E.

2011-01-01

This work concerns the electrochemical extraction of samarium from molten chlorides. In this way, the electrochemical behaviour of samarium ions has been investigated in the eutectic LiCl-KCl at the surface of tungsten, aluminium and aluminium coated tungsten electrodes. On a W inert electrode the electro-reduction of Sm(III) takes place in only one soluble-soluble electrochemical step Sm(III)/Sm(II). The electrochemical system Sm(II)/Sm(0) has not been observed within the electrochemical window, because of the prior reduction of Li(I) ions from the solvent, which inhibits the electro-extraction of Sm species from the salt on such a substrate. Sm metal in contact with the melt react to give Li(0) according to the reaction: Sm(0) + 2Li(I) ↔ Sm(II) + 2Li(0). On the contrary, on reactive Al electrodes the electrochemical system Sm(II)/Sm(0) was observed within the electroactive range. The potential shift of the redox couple is caused by the decrease of Sm activity in the metal phase due to the formation of Sm-Al alloys at the interface. The formation mechanism of the intermetallic compounds was studied in a melt containing: (i) both Sm(III) and Al(III) ions, using W and Al coated tungsten electrodes, and (ii) Sm(III) ions using an Al electrode. Analysis of the samples after potentiostatic electrolysis by X-ray diffraction and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), allowed the identification of Al 3 Sm and Al 2 Sm.

Electrochemical extraction of samarium from molten chlorides in pyrochemical processes

Energy Technology Data Exchange (ETDEWEB)

Castrillejo, Y., E-mail: ycastril@qa.uva.es [QUIANE/Dept Quimica Analitica, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Fernandez, P. [QUIANE/Dept Quimica Analitica, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Medina, J. [Dept Fisica Materia Condensada Cristalografia y Mineralogia, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain); Hernandez, P. [Centro de Investigaciones Quimicas, Universidad Autonoma del Estado de Hidalgo, Carr. Pachuca-Tulancingo Km. 4.5, C.P. 42076 Pachuca, Hidalgo (Mexico); Barrado, E. [QUIANE/Dept Quimica Analitica, F. de Ciencias, Universidad de Valladolid, Prado de la Magdalena s/n, 47005 Valladolid (Spain)

2011-10-01

This work concerns the electrochemical extraction of samarium from molten chlorides. In this way, the electrochemical behaviour of samarium ions has been investigated in the eutectic LiCl-KCl at the surface of tungsten, aluminium and aluminium coated tungsten electrodes. On a W inert electrode the electro-reduction of Sm(III) takes place in only one soluble-soluble electrochemical step Sm(III)/Sm(II). The electrochemical system Sm(II)/Sm(0) has not been observed within the electrochemical window, because of the prior reduction of Li(I) ions from the solvent, which inhibits the electro-extraction of Sm species from the salt on such a substrate. Sm metal in contact with the melt react to give Li(0) according to the reaction: Sm(0) + 2Li(I) {r_reversible} Sm(II) + 2Li(0). On the contrary, on reactive Al electrodes the electrochemical system Sm(II)/Sm(0) was observed within the electroactive range. The potential shift of the redox couple is caused by the decrease of Sm activity in the metal phase due to the formation of Sm-Al alloys at the interface. The formation mechanism of the intermetallic compounds was studied in a melt containing: (i) both Sm(III) and Al(III) ions, using W and Al coated tungsten electrodes, and (ii) Sm(III) ions using an Al electrode. Analysis of the samples after potentiostatic electrolysis by X-ray diffraction and scanning electron microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS), allowed the identification of Al{sub 3}Sm and Al{sub 2}Sm.

Measurements of rates of some reactions related to radiolytic effect on aqueous iodide solution

International Nuclear Information System (INIS)

Shiraishi, H.; Okuda, H.; Ishigure, K.

1986-01-01

A number of reactions takes place concurrently when aqueous iodide solution is subjected to radiation field. In order to help analyze this complicated radiation effect measurements of rate constants were undertaken for several important reactions. One of these concerns reduction of hypoiodous acid by hydrogen peroxide. For this reaction catalytic effect was found to be significant, and old rate data was revised. Measurements on reactions involving radicals were carried out by use of pulse radiolysis technique, which also include reexamination of results by previous workers. The reactions studied are (1) oxidation of iodide ion by hydroxyl radical (2) recombination reactions of atomic iodine and diiodide ion and (3) reduction of atomic and molecular iodine either by superoxide ion or by hydroperoxyl radical

ppt level detection of samarium(III) with a coated graphite sensor based on an antibiotic.

Science.gov (United States)

Ganjali, Mohammad Reza; Rezapour, Morteza; Pourjavid, Mohammad Reza; Haghgoo, Soheila

2004-07-01

N-[2-[4-[[[(Cyclohexylamino)carbonyl]amino]sulfonyl]phenyl]ethyl]-5-methyl pyrazine carboxamide (glipizid) was explored as an electro-active material for preparing a polymeric membrane-based sensor selective to samarium ions. The membrane incorporated 30% poly(vinyl chloride) (PVC), 53% benzyl acetate (BA), 11% glipizid and 6% sodium tetraphenyl borate. When coated on the surface of a graphite electrode, it exhibits Nernstian responses in the concentration range of 1.0 x 10(-5) to 1.0 x 10(-10) M, with a detection limit of 8.0 x 10(-11)M samarium. The electrode shows high selectivity towards samarium over several cations (alkali, alkaline earth, transition and heavy metal ions), and specially lanthanide ions. The proposed sensor has a very short response time (pH range for at least ten weeks. It was used as an indicator electrode in potentiometric titration of Sm(III) ions with an EDTA solution, and for determination of samarium in binary and ternary mixtures.

Preparation and biological behaviour of samarium-153-hydroxyapatite particles for radiation synovectomy

International Nuclear Information System (INIS)

Agrueelles, M.G.; Luppi Berlanga, I.S.; Torres, E.A.; Rutty Sola, G.A.; Rimoldi, G.

1998-01-01

The preparation and labelling procedures of 153 Sm-hydroxyapatite ( 153 Sm-HA) are described in this paper. Hydroxyapatite (HA) was prepared and studied as a radiosynovectomy agent. HA particles were prepared from the reaction of calcium nitrate and ammonia phosphate at high pH Samarium-153 labelling was done in two steps with citric acid. A serie of experimental conditions, such as specific activity, citric acid mass, radioactive solution volume, in-vitro stability, have been carried out. Radiolabelling efficiency was greater than 95%. In vitro studies showed high stability (≥99%). Animal studies showed a good retention in the synovium, with a very low extra-articular leakage over 6 days after administration. (author)

Adsorption and the initial stages of samarium condensation on iridium coated by graphite monolayer

International Nuclear Information System (INIS)

Abdullaev, R.M.; Tontegode, A.Ya.; Yusifov, F.K.

1978-01-01

Adsorption and the initial stages of vacuum samarium condensation on iridium coated by graphite monolayer (valent-saturated neutral substrate) were studied by the thermodesorption mass-spectrometry and thermoemission methods, and were compared with samarium adsorption and condensation on iridium. Desorption heat of samarium atoms with thin coating of Ir-C, equal to E approximately 1.9 eV has been determined. For desorption with Ir E is approximately 6 eV. Such a great difference in desorption heats is connected with the reduction of covalent constituent of adsorption bond in a neutral substrate. Samarium on Ir-C is found to be condensated in two states: loosely bound and tightly bound which sharply differ in properties. The tightly bound state is characterized by abnormally low vapour pressure. Possible nature of this state is discussed. Double effect on the condensation of the substrate valent saturation is noted. On the one hand, the reduction of the particle bond with the substrate decreases their concentration on the surface, preventing condensation. On the other hand, the release of the valent eloctrons of adatous brings about strong lateral interaction between them, which in its turn, promotes condensation during eased migration on the neutral substrate

Crystallization of Yttrium and Samarium Aluminosilicate Glasses

OpenAIRE

Lago, Diana Carolina; Prado, Miguel Oscar

2016-01-01

Aluminosilicate glasses containing samarium and yttrium (SmAS and YAS glasses) exhibit high glass transition temperatures, corrosion resistance, and glass stability on heating which make them useful for technological applications. Yttrium aluminosilicate glass microspheres are currently being used for internal selective radiotherapy of liver cancer. During the preparation process, crystallization needs to be totally or partially avoided depending on the final application. Thus knowing the cry...

Determination of 0.01–0.1% of samarium in 40–100 mg of lead chloride

NARCIS (Netherlands)

Agterdenbos, J.; Jütte, B.A.H.G.; Schuring, J.

1971-01-01

A method is described for the determination of 5–25 μg of samarium in about 40 mg of lead chloride, based on the removal of the lead by electrolysis and determination of the samarium by extraction with PAN and measurement of the extinction of the complex at 552 nm.

A redox-mediated chromogenic reaction and application in immunoassay.

Science.gov (United States)

Yu, Ru-Jia; Ma, Wei; Peng, Mao-Pan; Bai, Zhi-Shan; Long, Yi-Tao

2016-08-31

A novel redox-mediated chromogenic reaction was demonstrated based on the reaction between HAuCl4 and 2,2-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS), which generate various color responses from red to green in the resulting solutions. Various redox substance could be used to mediate the reaction and trigger a distinct color response. We established a sensitive hydrogen peroxide colorimetric sensor based on the redox-mediated chromogenic reaction and depicted the application both in detection of enzyme and in an immunoassay. Combining the traditional chromogenic reagent with gold nanoparticles, our assay has the advantage in short response time (within three minutes), high sensitivity (10(-12) g mL(-1) for HBsAg) and stability. Copyright © 2016. Published by Elsevier B.V.

Effect of samarium in corrosion and microstructure of Al-5Zn-0.5Cu as low driving voltage sacrificial anode

Science.gov (United States)

Pratesa, Yudha; Ferdian, Deni; Ramadhan, Fajar Yusya; Maulana, Bramuda

2018-05-01

Sacrificial Anode Low voltage is the latest generation of the sacrificial anode that can prevent the occurrence of Hydrogen Cracking (HIC) due to overprotection. The Al-5n-0.5Cu alloy showed the potential to be developed as the new sacrificial anode. However, the main problem is copper made Al2Cu intermetallic in grain boundary. Samarium is added to modify the shape of the intermetallic to make it finer and make the corrosion uniform. Several characterizations were conducted to analyze the effect of Samarium. Scanning electron microscope (SEM) and Energy dispersive spectroscopy was used to analyzed the microstructure of the alloy. Metallography preparation was prepared for SEM analysis. Corrosion behavior was characterized by cyclic polarization in 3.5% NaCl solution. The results show samarium can change the shape of intermetallic and refine the grains. In addition, samarium makes better pitting resistance and exhibits a tendency for uniform corrosion. It is indicated by the loop reduction (ΔEpit-prot). Current density increased as an effect of samarium addition from 6x10-5 Ampere (Al-5Zn-0.5Cu) to 2.5x10-4 Ampere (Al-5Zn-0.5Cu-0.5Sm). Steel potential protection increased after addition of samarium which is an indication the possibility of Al-Zn-Cu-Sm to be used as low voltage sacrificial anode.

Ultrasonic and viscosimetric studies of samarium laurate in benzene-dimethylsulfoxide mixtures

International Nuclear Information System (INIS)

Mehrotra, K.N.; Anis, M.

1995-01-01

Ultrasonic and viscosity measurements of samarium laurate in benzene-DMSO mixtures of different compositions (7:3 and 1:1 V/V) have been used to determine the critical micelle concentration (CMC), soap-solvent interaction, and various acoustic parameters of the system. The values of critical micelle concentration increase with increasing amount of DMSO in the solvent mixtures. The viscosity results have been explained on the basis of equations proposed by Einstein, Vand. Moulik, and Jones-Dole. The values of CMC for samarium laurate obtained from the viscosity measurements are in agreement with the results obtained from ultrasonic measurements. The results show that the soap molecules do not aggregate appreciably below CMC there is a marked change in the aggregation behaviour at CMC. (author)

Behavior of Samarium III during the sorption process; Comportamiento del Samario-III durante el proceso de sorcion

Energy Technology Data Exchange (ETDEWEB)

Ordonez R, E.; Garcia G, N.; Garcia R, G. [ININ, Carr. Mexico-Toluca Km 36.5, Salazar, Estado de Mexico (Mexico)]. e-mail: edo@nuclear.inin.mx

2004-07-01

In this work the results of the behavior of samarium in solution are presented, in front of a fine powder of zirconium silicate (zircon). For that which is necessary to characterize the zircon, studying the crystallinity, the morphology, the surface area and the isoelectric point. The behavior of samarium in solution is studied by means of the elaboration of isotherm of sorption, using the technique by lots. One observes that to pH values of nearer to the isoelectric point (pH = 7.23) the process of sorption of the samarium begins, reaching a maximum to near pH at 9. The technique of luminescence is used to determine the concentration of the sipped samarium (phosphorescence) and also to make the speciation of the species formed in the surface of the zircon (phosphorescence). The results can be extrapolated with the plutonium when making the modeling of the migration of alpha emitting coming from the repositories of radioactive waste since both they have similar chemical properties (they are homologous). (Author)

Inductively coupled plasma optical emission spectrometry analysis of lanthanum, samarium and gadolinium oxides for rare earths impurities

International Nuclear Information System (INIS)

Reino, L.C.P.; Lordello, A.R.

1990-09-01

An inductively coupled plasma optical emission spectrometry method is described for the determination of Sm, Eu, La, Gd, Dy, Pr, Ho, Nd, Tb and Y in purified oxides of lanthanum, samarium and gadolinium. The method enables a simple, precise and readily available determination. Dissolution of the samples is achieved with diluted hydrochloric acid (1:1). The solutions are diluted to volume for a concentration of 1mg/ml. The lowest determination limit is 0,01% for most elements and 0,05 or 0,1% for a few rare earths in samarium and gadolinium matrices. Lanthanum, Samarium and Gadolinium concentrates with purity grade of 99,9%, 99,6% and 99,8%, respectively, can be analysed by this procedure. (author)

Enhancement of the fluorescence of the samarium (III) complex by gadolinium (III)

International Nuclear Information System (INIS)

Yun-Xiang, C.; Zhang-Hua, L.

1988-01-01

The increase in sensitivity and selectivity of reactions in which colored species are formed by the addition of different metal ions is an area of research that has recently been developed. This phenomenon, which is sometimes called cocolaration effect, has been explained by the formation of mixed metal complex. The authors found an analogous phenomenon of reactions forming fluorescent complexes. The complexes of Sm(III)-thenoyltrifluoroacetone (TTA)-phenanthroline (Phen)-Triton-X-100 (TX-100) and Gd(III) (or La(III), Lu(III) and Y(III))-TTA-Phen-TX-100 had practically no fluorescence separately. Instead, a fluorescence-enhancement phenomenon caused by adding Gd or La, Lu and Y ions to the system was observed for the first time. The intensity of the enhanced fluorescence of Sm(III) complex was increased in the following order: La< Y< Lu< Gd. By analogy with cocoloration effect, the authors call this new fluorescence-enhancement phenomenon the co-fluorescence effect. The object of this work was to study the enhancement effect of Gd(III) on the fluorescence of the Sm(III)-TTA-Phen-TX-100 system. The recommended fluorimetric method has been applied to the determination of trace amounts of samarium in ytterbium oxide with satisfactory results. A general reaction mechanism for the system studied was proposed

Pemisahan Unsur Samarium dan Yttrium dari Mineral Tanah Jarang dengan Teknik Membran Cair Berpendukung (Supported Liquid Membrane

Directory of Open Access Journals (Sweden)

Amri Amin

2009-06-01

Full Text Available he increasing use of rare earth elements in high technology industries needs to be supported by developmental work for the separation of elements. The research objective is fiercely attracting and challenging considering the similarity of bath physical and chemical properties among these elements. The rate separation of samarium and yttrium elements using supported liquid membrane has been studied. Polytetrafluoroethylene (PTFE with pore size of 0.45 µm has been used as the membrane and di(2-ethylhexyl phosphate (D2EHP in hexane has been used as a carrier and nitric acid solution has been used as receiving phase. Result of experiments showed that the best separation rate of samarium and yttrium elements could be obtained at feeding phase of pH 3.0, di(2-ethylhexyl phosphate (D2EHP concentration of 0.3 M, agitation rate of 700 rpm, agitation time of 2 hours, and nitric acid and its solution concentrations of 1.0 M and 0.1 M, respectively. At this condition, separation rates of samarium and yttrium were 64.4 and 67.6%, respectively.   Keywords: liquid membrane, rare earth elements, samarium, yttrium

Preparation and examination of properties of samarium-153-EDTMP complex

International Nuclear Information System (INIS)

Nowak, M.; Garnuszek, P.; Lukasiewicz, A.; Wozniak, I.; Zulczyk, W.; Licinska, I.

1995-01-01

Preparation and properties of ethylenediaminetetramethylenephosphonic acid (EDTMP) as well as some properties of 153 Sm-EDTMP chelate have been examined. The chelate formed by samarium-153 (46.3 h, β - -decay) with EDTMP exhibits high bone uptake and can be used for treatment of disseminated, painful skeletal metastases. The purity and stability of solutions of 153 Sm-EDTMP chelate were examined in a broad range of samarium concentration and 153 Sm specific activity. The complex under study was examined by radio-TLC, -electrophoresis and radio-HPLC. The results obtained suggest the small size of molecules of 153 Sm-EDTMP chelate as compared with molecules of ''free''EDTMP. The results of biodistribution of 153 Sm-EDTMP determined in rats indicate the quick blood clearance, high deposition of radioactivity in bone and quick excretion of radioactivity into urine. No specific uptake of 153 Sm-EDTMP in extra-skeletal organs was found. (author). 42 refs, 13 figs, 22 tabs

Expedient Method for Samarium(II) Iodide Preparation Utilizing a Flow Approach

Czech Academy of Sciences Publication Activity Database

Voltrová, Svatava; Šrogl, Jiří

2013-01-01

Roč. 24, č. 3 (2013), s. 394-396 ISSN 0936-5214 R&D Projects: GA MŠk LH12013 Institutional support: RVO:61388963 Keywords : flow * samarium * iodide * reduction Subject RIV: CC - Organic Chemistry Impact factor: 2.463, year: 2013

Optical properties of zinc–vanadium glasses doped with samarium ...

Indian Academy of Sciences (India)

Abstract. Zinc–vanadium glasses doped with samarium oxide having the chemical composition Sm2O3(x). ZnO(40−x)V2O5(60)(where x = 0·1–0·5 mol%) were prepared by melt quenching method. The density of these glasses was measured by Archimedes method; the corresponding molar volumes have also been ...

Oklo natural reactor. Study of uranium and rare earths migration on a core drilled through a reaction zone. Application to determination of the date of the nuclear reaction by measurement of fission products

International Nuclear Information System (INIS)

Ruffenach, J.C.

1977-01-01

Isotopic and chemical analysis of uranium and five rare earths: neodymium, samarium, europium, gadolinium and dysprosium were effected on fourteen samples taken in the same core drilled through a reaction zone of the Oklo uranium deposit. This study points out the general stability of uranium and fission rare earths; spatial distributions of these elements are quite analogous. Migrations have affected about 5% only of fission neodymium in the core of the reaction zone; corresponding values for samarium and gadolinium are slightly higher. These migration phenomena have carried rare earths to no more than 80 cm out of the core. By study of the europium it is shown that nuclear reactions have stayed in the ground since the time of reactions. On the other hand it is shown by analysis of the dysprosium that rare earths have not undergone an important movement. This study allow also the datation of nuclear reactions from the measurement of the quantity of fission neodymium produced. A value of 1.98x10 9 years is obtained slightly higher than the value obtained by geochronology [fr

X-ray spectrum in the range (6-12) A emitted by laser-produced plasma of samarium

International Nuclear Information System (INIS)

Louzon, Einat; Henis, Zohar; Levi, Izhak; Hurvitz, Gilad; Ehrlich, Yosi; Fraenkel, Moshe; Maman, Shlomo; Mandelbaum, Pinchas

2009-01-01

A detailed analysis of the x-ray spectrum emitted by laser-produced plasma of samarium (6-12 A) is presented, using ab initio calculations with the HULLAC relativistic code and isoelectronic considerations. Resonance 3d-nf (n=4 to 7), 3p-4d, 3d-4p, and 3p-4s transitions in Ni samarium ions and in neighboring ionization states (from Mn to Zn ions) were identified. The experiment results show changes in the fine details of the plasma spectrum for different laser intensities.

Synthesis of samarium binding bleomycin - a possible NCT radiosensitizer

Energy Technology Data Exchange (ETDEWEB)

Mendes, B.M., E-mail: bmm@cdtn.b [Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN-MG), Belo Horizonte, MG (Brazil); Mendes, T.M.; Campos, T.P.R., E-mail: campos@nuclear.ufmg.b [Universidade Federal de Minas Gerais (UFMG), Belo Horizonte, MG (Brazil)

2011-07-01

Bleomycin (BLM) is a drug that has attractive features for the development of a new radiopharmaceutical, particularly with regard to neutron capture therapy (NCT) sensitized by Sm-149. It has the ability to chelate many metal ions. In vitro studies have shown that up to 78% of BLM present in a cell is accumulated inside the nucleus or in the nuclear membrane. In addition, this drug has higher affinity for tumor tissues than for normal tissues. Radioactive isotopes carried by this antibiotic would be taken preferentially to one important cellular targets DNA. Besides, BLM displays intrinsic anti-tumor activity - it is a chemotherapic antibiotic clinically used against some cancers. This study aimed to obtain bleomycin molecules bound to samarium (BLM-Sm) for NCT studies in vitro and in vivo. The binding technique employed in this work has great simplicity and low cost. Thin layer chromatography, high performance liquid chromatography, fast protein liquid chromatography and analysis by ICP-AES were applied to verify the binding molecule. ICP-AES results showed the presence of samarium in the sample peaks related to BLM-Sm. However, efficiency and stability of this bond needs to be investigated. (author)

Synthesis of samarium binding bleomycin - a possible NCT radiosensitizer

International Nuclear Information System (INIS)

Mendes, B.M.; Mendes, T.M.; Campos, T.P.R.

2011-01-01

Bleomycin (BLM) is a drug that has attractive features for the development of a new radiopharmaceutical, particularly with regard to neutron capture therapy (NCT) sensitized by Sm-149. It has the ability to chelate many metal ions. In vitro studies have shown that up to 78% of BLM present in a cell is accumulated inside the nucleus or in the nuclear membrane. In addition, this drug has higher affinity for tumor tissues than for normal tissues. Radioactive isotopes carried by this antibiotic would be taken preferentially to one important cellular targets DNA. Besides, BLM displays intrinsic anti-tumor activity - it is a chemotherapic antibiotic clinically used against some cancers. This study aimed to obtain bleomycin molecules bound to samarium (BLM-Sm) for NCT studies in vitro and in vivo. The binding technique employed in this work has great simplicity and low cost. Thin layer chromatography, high performance liquid chromatography, fast protein liquid chromatography and analysis by ICP-AES were applied to verify the binding molecule. ICP-AES results showed the presence of samarium in the sample peaks related to BLM-Sm. However, efficiency and stability of this bond needs to be investigated. (author)

Influence of pretreatment temperature cycling on the radiating defect formation in silicon doped by samarium

International Nuclear Information System (INIS)

Abdurakhmanov, K.P.; Nazyrov, D.E.

2006-01-01

Full text: The raise of thermal and radiation stability as it is known, is one of actual problems of physics semiconductors. Recently it is established, that the rare-earth elements (REE) raise a stability of silicon to exterior action. In this connection the investigation of silicon doped REE by samarium and influence on its properties of heat treatments and radiation exposure is important. In sectional operation the outcomes of investigations of influence of samarium on thermal (600 degree C are reduced; 600 deg. + 900 deg. C; 900 deg. C; 900 deg. C + 600 deg. C; 1100 deg. C; 600 deg. C + 900 deg. C + 1100 deg. C; 900 deg. C + 600 deg. C + 1100 deg. C) thermal defect formation and radiation defect formation (exposure of γ-quanta 60 Co) both in beforehand wrought, and in thermally unfinished samples. After each cycle of heat treatments samples cool fast (throwing off in oil) or slowly (together with the furnace). Doping n-silicon REE by gadolinium and samarium was carried out during cultivation. The concentration of gadolinium and samarium in silicon, on sectional of a neutron-activation analysis was equaled 10 14 - 10 18 cm -3 . As control is model monocrystal silicon such as KEP-15/50. Para-meters of deep levels originating in control and doped REE samples, both past heat treatment or temperature cycling, and irradiated by the γ-quanta are defined by methods of a capacity spectroscopy: DLTS and IRC. The obtained outcomes have shown, that in irradiated with the γ-quanta 60 Co deep levels samples are formed with energies: E C -0,17 eV, E C -0,32 eV, EC-0,41 eV. Thus the parameters of deep levels vary depending on requirements of prestress heat treatment. For example heat treatment at 600 deg. C essentially increments a velocity of introduction of and centre (deep level of E C -0,17 eV), in comparison with a velocity of introduction of this level in samples with prestress heat treatment at 900 deg. C. In samples n-Si doped by samarium effectiveness of formation

Sorption of samarium in iron (II) and (III) phosphates in aqueous systems

International Nuclear Information System (INIS)

Diaz F, J.C.

2006-01-01

The radioactive residues that are stored in the radioactive confinements its need to stay isolated of the environment while the radioactivity levels be noxious. An important mechanism by which the radioactive residues can to reach the environment, it is the migration of these through the underground water. That it makes necessary the investigation of reactive materials that interacting with those radionuclides and that its are able to remove them from the watery resources. The synthesis and characterization of materials that can be useful in Environmental Chemistry are very important because its characteristics are exposed and its behavior in chemical phenomena as the sorption watery medium is necessary to use it in the environmental protection. In this work it was carried out the sorption study of the samarium III ion in the iron (II) and (III) phosphate; obtaining the sorption isotherms in function of pH, of the phosphate mass and of the concentration of the samarium ion using UV-visible spectroscopy to determine the removal percentage. The developed experiments show that as much the ferrous phosphate as the ferric phosphate present a great affinity by the samarium III, for what it use like reactive material in contention walls can be very viable because it sorption capacity has overcome 90% to pH values similar to those of the underground and also mentioning that the form to obtain these materials is very economic and simple. (Author)

Synthesis of 11C-labelled haloalkanonitriles and examples of their use in some alkylation reactions

International Nuclear Information System (INIS)

Hoernfeldt, K.; Antoni, G.; Laangstroem, B.

1992-01-01

The synthesis of the 11 C-labelled bifunctional precursors 4-iodobutyro[ 11 C]nitrile (1), 4-tosyloxybutyro[ 11 C]nitrile (2), 5-iodovalero[ 11 C]nitrile (3), 5-toxyloxyvalero[ 11 C]nitrile (4) and 4-bromopentano[ 11 C]nitrile (5) are presented. The nucleophilic substitution reactions of [ 11 C]cyanide with dibromides, diiodides, ditosylates or mixed iodotosylates producing 1-5 have been carried out in different solvents and the labelled products were obtained in 62-98% radiochemical yields (not isolated), with a total synthesis time of 5 min counted from the end of the hydrogen [ 11 C]cyanide synthesis. The labelled haloalkanonitriles 1 and 3 have also been used in some alkylation reactions with various carbon and oxygen nucleophiles. (au)

Elucidation of reactive wavepackets by two-dimensional resonance Raman spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Guo, Zhenkun; Molesky, Brian P.; Cheshire, Thomas P.; Moran, Andrew M., E-mail: ammoran@email.unc.edu [Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599 (United States)

2015-09-28

Traditional second-order kinetic theories fail to describe sub-picosecond photochemical reactions when solvation and vibrational dephasing undermine the assumption of equilibrium initial conditions. Four-wave mixing spectroscopies may reveal insights into such non-equilibrium processes but are limited by the single “population time” available in these types of experiments. Here, we use two-dimensional resonance Raman (2DRR) spectroscopy to expose correlations between coherent nuclear motions of the reactant and product in the photodissociation reaction of triiodide. It is shown that the transition of a nuclear wavepacket from the reactant (triiodide) to product (diiodide) states gives rise to a unique pattern of 2DRR resonances. Peaks associated with this coherent reaction mechanism are readily assigned, because they are isolated in particular quadrants of the 2DRR spectrum. A theoretical model in which the chemical reaction is treated as a vibronic coherence transfer transition from triiodide to diiodide reproduces the patterns of 2DRR resonances detected in experiments. These signal components reveal correlation between the nonequilibrium geometry of triiodide and the vibrational coherence frequency of diiodide. The 2DRR signatures of coherent reaction mechanisms established in this work may generalize to studies of ultrafast energy and charge transfer processes.

Statistical properties of multistep enzyme-mediated reactions

OpenAIRE

de Ronde, Wiet H.; Daniels, Bryan C.; Mugler, Andrew; Sinitsyn, Nikolai A.; Nemenman, Ilya

2008-01-01

Enzyme-mediated reactions may proceed through multiple intermediate conformational states before creating a final product molecule, and one often wishes to identify such intermediate structures from observations of the product creation. In this paper, we address this problem by solving the chemical master equations for various enzymatic reactions. We devise a perturbation theory analogous to that used in quantum mechanics that allows us to determine the first () and the second (variance) cumu...

Impact of educational strategies in positioning Samarium-153 EDTMP as a treatment for metastatic bone pain

International Nuclear Information System (INIS)

Seminario, C.; Morales, R.; Castro, M.; Cano, R.A.; Mendoza, G.

2005-01-01

To educate is a difficult task but its results make efforts worthwhile. Many patients in Peru suffer from intractable bone pain due to metastases. Since 1993 radionuclides were used to palliate bone pain due to metastases in Peru. First, with the help of the IAEA, Peru participated in a clinical trial using Phosphorus 32 and Strontium 89. Then, efforts were performed to produce Samarium 153 EDMTP locally, which was achieved in 1995. Nevertheless, years passed and Samarium use did not increase proportionally to the needs of people with cancer and bone pain, mainly the poor. Educational strategies have been proven useful for delivering solutions to many health problems in other diseases and also in cancer. Health education makes patients and their relatives assume responsible care of their problems. The purpose of this work was to increase Samarium EDTMP use as palliative treatment in patients with bone pain due to metastases, using educational strategies as means to change attitudes towards this health problem. In September 2003, a task group conducted studies in order to apply several methods to achieve the goal of increasing Samarium EDTMP use. Educational strategies employed were performed to provide verbal and written information to patients, physicians, medical students, residents, pain specialists, oncologists and neurologists, as well as general public. Verbal information included radio interviews, television spots and a phone number (in charge of two secretaries, prepared for answering and if not possible, a physician was in charge of attending patient consultation), e-mail and a web page for consultation. Written material was delivered to several newspapers, including clinical use of Samarium, possibilities of being elected for treatment, benefits and risks and a photography of the product. Politics of the institution producing Samarium changed, in order to achieve minimum cost of the product and it was delivered to all publics at the lowest cost for a year

Lanthanum (samarium) nitrate-4-aminoantipyrine nitrate-water systems

International Nuclear Information System (INIS)

Starikova, L.I.; Zhuravlev, E.F.

1985-01-01

Using the isothermal method of cross-sections at 50 deg C systems lanthanum nitrate-4-aminoantipyrine nitrate-water (1), samarium nitrate-4-aminoantipyrine nitrate-water (2), are studied. Isotherms of system 1 consist of two crystallization branches of initial salt components. In system 2 formation of congruently soluble compounds of the composition Sm(No) 3 ) 3 xC 11 H 13 ON 3 xHNO 3 is established. Analytical, X-ray phase and thermogravimetric analysis of the isolated binary salt are carried out

Collective effects in even-mass samarium isotopes by polarized-proton scattering

NARCIS (Netherlands)

Petit, R.M.A.L.; Hall, van P.J.; Klein, S.S.; Moonen, W.H.L.; Nijgh, G.J.; Overveld, van C.W.A.M.; Poppema, O.J.

1993-01-01

The even-mass samarium isotopes 148,...,152Sm have been investigated by polarized proton scattering at 20.4 MeV beam energy. The data have been analysed with an 'extended' optical model, where the intensities of the first maxima of the main inelastic channels are fitted in a coupled-channels

Memory effect of calcined layered samarium hydroxy chlorides in aqueous solution

International Nuclear Information System (INIS)

Lee, Byung Il; Byeon, Song Ho

2015-01-01

The decomposition and recovery behavior of layered samarium hydroxychloride (Sm 2 (OH) 5 Cl·nH 2 O, LSmH) has been closely studied in various conditions. Although the heat treatment of LSmH at 700 °C completely collapsed typical layered structure, the calcined LSmH (c-LSmH) recovered its layered characteristics and consequently its ability to intercalate anions into the interlayer space when it was rehydroxylated and rehydrated in aqueous solutions containing organic and inorganic anions. This phenomenon is similar to the memory effect observed in classical layered double hydroxides (LDHs), where LDHs calcined to a mixture of metal oxides can recover their layered structures in aqueous solutions. In contrast, the recovery reaction of c-LSmH in water without any counter anions was unsuccessful and instead resulted in the formation of Sm(OH) 3 . Such a difference was interpreted on the basis of the salt effect on Sm 2 (OH) 5 Cl·nH 2 O–Sm(OH) 3 phase equilibria in water

Sorption-desorption of samarium in Febex bentonite

International Nuclear Information System (INIS)

Ramirez-Guinart, O.; Rigol, A.; Vidal, M.; Fernandez-Poyatos, P.; Alba, M. D.

2012-01-01

Document available in extended abstract form only. The chemical and physical nature of the clay is a key issue in the design of engineered barriers. The FEBEX bentonite is one of the clays candidates to be used in engineered barriers in deep geology repositories (DGR). Here, its performance was tested with respect to the sorption-desorption of samarium, which is a lanthanide that, besides being considered as a natural analogue of actinides, may also be present in high level radioactive waste in the form of the radioactive isotope 151 Sm. FEBEX bentonite was used in this study. This is a di-octahedral smectite, with isomorphic substitutions in tetrahedral and octahedral sheets. Its theoretical cation exchange capacity value is 1500 meq kg -1 . Sorption isotherms were obtained for Sm in the range of initial concentrations of 0.01 and 9 meq l -1 . Tests were carried out in deionized water and in a medium simulating the composition of interstitial water. Sorption tests were performed equilibrating 30 ml of the Sm solution with 0.2 g of clay. After a contact time of 24 hours, supernatants were decanted off after centrifugation. The quantification of the concentration of Sm in the initial and final solutions allowed us to quantify the Sm equilibrium concentration (C eq ), the fraction sorbed in the FEBEX bentonite (C sorb ) and to derive the sorption K d data. Desorption tests were applied to determine the desorption K d and the percentage of Sm reversibly sorbed. Desorption tests were performed with the bentonite residue from the sorption step, under the same experimental conditions, but without Sm. Powder X-ray diffractograms were obtained from 3 to 70 deg. 2θ with a step of 0.05 deg. and a counting time of 3 s. The crystalline phases were identified using the computer program X'Pert HighScore. The morphology of the samples was analyzed by SEM at 20 kV. An EDX system was fitted to the SEM equipment to perform chemical analyses of the samples using a Si/Li detector

IgE-mediated reaction to local anaesthetics

International Nuclear Information System (INIS)

Kartal, O.; Gulec, M.; Sener, O.; Caliskaner, A.Z.

2013-01-01

Local anaesthetics (LAs) are essential agents in daily practices of dentistry, minor surgery and dermatology. Although they have an impressive history of safety and efficacy, LAs also have the potential to produce adverse events, which are mainly of non-immune nature. The true IgE-mediated allergies are quite rare, but are more considerable in terms of ability to cause life-threatening outcomes. In this report, we present a case of IgE-mediated systemic reaction to LAs occurring during epidural anaesthesia for Cesarean section. (author)

Laser spectroscopy of atomic samarium

International Nuclear Information System (INIS)

Barkov, L.M.; Melik-Pashaev, D.A.; Zolotorev, M.S.

1988-01-01

Samarium spectrum was studied with a purpose to find transitions to be used in experiments on parity nonconservation. Macaluso-Corbino effect - Faraday rotation near resonance was used for the search and study of spectral lines. We have identified previously unknown energy levels belonging to the 4f 5 6s 2 5 D term: 15914.55(3) cm -4 (J=1), 17864.29(3) cm -4 (J=2), 20195.76(3) cm -4 (J=3). M1-transitions to these levels from the levels of the ground 4f 5 6s 2 7 F term were observed. There are several peculiarities of these transitions which are due to the fact that they occut within an inner 4f 5 -shell, particularly, a very small presuure broadening by inert gases. 44 refs.; 17 figs.; 7 tabs

Removal of trivalent samarium from aqueous solutions by activated biochar derived from cactus fibres

Institute of Scientific and Technical Information of China (English)

Loukia Hadjittofi; Styliana Charalambous; Ioannis Pashalidis

2016-01-01

The efficiency of activated biochar fibres obtained fromOpuntia Ficus Indica regarding the sorption of trivalent samarium (Sm(III)) from aqueous solutions was investigated by batch experiments. The effect of various physicochemical parameters (e.g. pH, initial metal concentration, ionic strength, temperature and contact time) on the Sm(III) adsorption was studied and the surface species were characterized by FTIR spectroscopy prior to and after the lanthanide sorption. The experimental results showed that the acti-vated biochar fibres possessed extraordinary sorption capacity for Sm(III) in acidic solutions (qmax=90 g/kg, pH 3.0) and near neutral solutions (qmax=350 g/kg, pH 6.5). This was attributed to the formation of samarium complexes with the surface carboxylic moieties, available in high density on the lamellar structures of the bio-sorbent.

Flow Giese reaction using cyanoborohydride as a radical mediator

Directory of Open Access Journals (Sweden)

Takahide Fukuyama

2013-09-01

Full Text Available Tin-free Giese reactions, employing primary, secondary, and tertiary alkyl iodides as radical precursors, ethyl acrylate as a radical trap, and sodium cyanoborohydride as a radical mediator, were examined in a continuous flow system. With the use of an automated flow microreactor, flow reaction conditions for the Giese reaction were quickly optimized, and it was found that a reaction temperature of 70 °C in combination with a residence time of 10–15 minutes gave good yields of the desired addition products.

Comparison of polymerase chain reaction (PCR) and loop-mediated ...

African Journals Online (AJOL)

Comparison of polymerase chain reaction (PCR) and loop-mediated isothermal amplification (LAMP) for diagnosis of Fusarium solani in human immunodeficiency virus (HIV) positive patients. ... The test was carried out in 1 h reaction at 65°C in a heater block. The specificity of the test was 100% and its sensitivity was a ...

Pressure and irradiation effects on transport properties of samarium compounds with instable valence

International Nuclear Information System (INIS)

Morillo, J.

1981-01-01

Electron transport properties in samarium compounds with instable valence are studied in this thesis: from SmS in its integer valence phases at common pressure to SmB 6 compound IV at common pressure through SmSsub(1-x)Psub(x) (x 6 is presented [fr

Synthesis of samarium complexes with the derivative binder of Schiff Quinolinic base. Characterization and photophysical study; Sintesis de complejos de samario con el ligante derivado de base de Schiff Quinolinica. Caracterizacion y estudio fotofisico

Energy Technology Data Exchange (ETDEWEB)

Lucas H, J.

2016-07-01

In this work we determined the metal: binder stoichiometry of the species formed during the UV/Vis spectrophotometric titration of the derivative binder of Schiff quinolinic base, L1 with the samarium nitrate pentahydrate in methanol. Statistical analysis of the data allowed proposing the metal: binder stoichiometry for the synthesis of the complexes which was one mole of samarium salt by 2.5 moles of binder and thus favor the formation of complexes with 1M: 1L and 1M: 2L stoichiometries. They were synthesized in aqueous-organic medium (water-ethanol), isolated and purified two complexes with stoichiometry 1 Sm: 1 L1, complex 1 and 1 Sm: 2 L1, complex 2. The overall yield of the reaction was 76%. The characterization of the formed complexes was performed by visible ultraviolet spectrometry (UV/Vis), nuclear magnetic resonance, X-ray photoelectron spectroscopy (XP S), thermal gravimetric analysis with differential scanning calorimetry (TGA/DSC), and radial distribution function. These complexes were studied by fluorescence and emission phosphorescence at variable temperature. Spectroscopic techniques used in both solution and solid demonstrated the formation and stability of these complexes. In addition XP S indicated that in both complexes the samarium retains its oxidation state 3+. Luminescence studies indicated that there is intra-binding charge transfer which decreases the transfer of light energy from the binder to the samarium. Based on the experimental results, L1 binder molecules and complexes 1 and 2 were modeled that demonstrated the proposed Nc for each complex, as well as allowed to visualize the structural arrangement of the molecules, complexes and binder. (Author)

Graphite furnace atomic absorption spectrometry with a tantalum boat for the determination of yttrium, samarium, and dysprosium in a mish metal

International Nuclear Information System (INIS)

Daidoji, Hidehiro; Tamura, Shohei

1982-01-01

The determination of yttrium, samarium, and dysprodium by means of graphite-furnace atomic absorption spectrometry (AAS) was studied by a tantalum boat inserted into a graphite tube atomizer. These elements could not be determined by the use of a commercial graphite tube, In the atomization from a tantalum boat, better analytical sensitivities and negligible memory effects for these rare earths are obtained. The analytical sensitivities of yttrium, samarium, and dysprodium with the tantalum boat were 0.60 ng, 0.86 ng, and 0.17 ng respectively. This method was applied for the determination of yttrium, samarium, and dysprosium in a mish metal. The measurements were performed with slightly acidified solutions (0.01 mol dm 3 HCI or HNO 3 ). The sensitivities and the precisions for these elements decreased with increasing acid concentration. An enhancement in the sensitivities of yttrium and dysprosium upon the addition of a large excess of lanthanum, neodymium, and praseodymium salts were observed. The yttrium, samarium, and dysprosium in a mish metal were determined with both analytical curves of standard solutions containing an excess of lanthanum, cerium, and neodymium ions and of the standard addition. The precisions for this work were in the 3 - 9.3% range. (author)

Peculiarities of electronic, phonon and magnon subsystems of lanthanum and samarium tetraborides

Energy Technology Data Exchange (ETDEWEB)

Novikov, V.V., E-mail: vvnovikov@mail.ru; Mitroshenkov, N.V.; Matovnikov, A.V.

2015-10-15

Experimental research was carried out to study the temperature dependences of heat capacity C{sub p}(T = 2–300 K), lattice parameters a(T), and ≿(T), (5–300 K) of lanthanum and samarium tetraborides. A comparison with data obtained previously for LuB{sub 4} reveals the peculiar influence of lanthanide contraction and the rare-earths mass on the thermodynamic properties of rare earth tetraborides at low and high temperatures. Sharp anomalies were found in the heat capacity and thermal expansion for SmB{sub 4} at T{sub N} = 25.1 K, conditioned by the phase transition into antiferromagnetic state. The more poorly defined heat capacity anomaly around 7 K is referred to the quadrupole orbital fluctuation of the atomic magnetic moments for Sm{sup 3+} ions. The electronic, lattice, and magnetic contributions to the heat capacity and thermal expansion of samarium tetraboride were defined. Our approach makes it possible to adequately approximate the lattice components of heat capacity and thermal expansion by combining the Debye and Einstein contributions, which are based on the joint analysis of calorimetric and X-ray data. The influence of the frustration of the atomic magnetic moment system for Sm{sup 3+} ions on the thermodynamic characteristics of the samarium tetraboride magnetic phase transition was revealed. - Highlights: • The heat capacity and lattice parameters for LaB{sub 4} and SmB{sub 4} were determined at 2–300 K. • The anomalies of C{sub p}(T), a(T), c(T) for SmB{sub 4} due to the phase transition are revealed. • The lattice contributions to the thermal properties of LaB{sub 4} and SmB{sub 4} are analyzed.

Ekstraksi Pemisahan Neodimium dari Samarium, Itrium dan Praseodimium Memakai Tri Butil Fosfat

Directory of Open Access Journals (Sweden)

Maria Veronica Purwani

2017-05-01

Full Text Available The extraction of Nd(OH3 (neodymium hydroxide concentrate containing Y (yttrium, Sm (samarium and Pr (praseodymium as product of monazite processed has been done. The purpose of this study is to determine the separation of Nd from Y, Pr and Nd Sm in Nd concentrate. The aqueous phase was concentrated Nd (OH3 in HNO3 and extractant while organic phase was Tri Butyl Phosphate (TBP in kerosene. Parameters studied were pH and concentration feed, concentration of TBP in kerosene, extraction time and stirring speed. The result showed that the optimization of separation extraction neodymium from samarium, yttrium and praseodymium in Nd(OH3 concentrated with TBP, obtained the optimum condition of pH = 0.2, concentration of feed 100 g /L, concentration of TBP in kerosene 5%, extraction time 15 minutes and stirring speed 150 rpm. With the conditions, Separation Factor (SF obtained for Nd-Y, Nd-Pr, Nd-Sm are 2.242, 4.811, 4.002 respectively, while D and extraction efficiency of Nd are 0.236 and 19.07%.

Reaction mechanisms of ruthenium tetroxide mediated oxidations of organic compounds

Energy Technology Data Exchange (ETDEWEB)

Froehaug, Astrid Elisabeth

1995-12-31

This thesis reports a study of the mechanism of ruthenium tetroxide mediated oxidations of saturated hydrocarbons, ethers, alkenes and alcohols. Several methods were used. The RuO{sub 4}-mediated oxidations of adamantane and cis-decalin were studied in CCl{sub 4}-CH{sub 3}CN-H{sub 2}O and in acetone-water. The rate of reaction was found to be moderately influenced by the polarity of the solvent. Solvent properties other than the polarity were also found to influence the reaction rates. From the oxidations of adamantane and adamantane-1,3,5,7-d{sub 4} two primary kinetic deuterium isotope effects were found. These were comparable with the deuterium isotope effects found for the analogous oxidations of cis-decalin and cis-decalin-d{sub 18}. The results seem to exclude both a one step hydride abstraction reaction mechanism and a one step concerted mechanism, as well as a scheme where two such mechanisms compete. The observations may be explained by a two step reaction mechanism consisting of a pre-equilibrium with formation of a substrate-RuO{sub 4} complex followed by a concerted rate determining reaction. The RuO{sub 4}-mediated oxidation of ethers was of kinetic second order with a small enthalpy of activation and a large negative entropy of activation. Oxidation of cyclopropylmethyl methyl ether gave methyl cyclopropanecarboxylate, no rearranged products were observed. On RuO{sub 4} oxidations in CCl{sub 4} with NaIO{sub 4} as stoichiometric oxidant, no chlorinated products were observed. Several observations not in agreement with a hydride or a hydrogen abstraction mechanism may be explained by assuming that the reaction proceeds by either a concerted reaction or by a reversible oxidative addition of the ether to RuO{sub 4} followed by a slow concerted step. 228 refs., 9 figs., 27 tabs.

Pyroelectric properties and electrical conductivity in samarium doped BiFeO 3 ceramics

KAUST Repository

Yao, Yingbang

2012-06-01

Samarium (Sm 3+) doped BiFeO 3 (BFO) ceramics were prepared by a modified solid-state-reaction method which adopted a rapid heating as well as cooling during the sintering process. The pyroelectric coefficient increased from 93 to 137 μC/m 2 K as the Sm 3+ doping level increased from 1 mol% to 8 mol%. Temperature dependence of the pyroelectric coefficient showed an abrupt decrease above 80 °C in all samples, which was associated with the increase of electrical conductivity with temperature. This electrical conduction was attributed to oxygen vacancy existing in the samples. An activation energy of ∼0.7 eV for the conduction process was found to be irrespective of the Sm 3+ doping level. On the other hand, the magnetic Néel temperature (T N) decreased with increasing Sm 3+ doping level. On the basis of our results, the effects of Sm doping level on the pyroelectric and electrical properties of the BFO were revealed. © 2011 Elsevier Ltd. All rights reserved.

Australian manufacture of QuadrametTM (Samarium-153 EDTMP)

International Nuclear Information System (INIS)

Wood, N.R.; Whitwell, J.

1997-01-01

Quadramet T (Samarium-153 EDTMP) has been shown overseas to be potentially useful in the palliation of painful osteoblastic skeletal metastases and has been approved this year for general marketing in the USA. Australian Radioisotopes (ARI) has licensed this product from the Australian patent holders, Dow Chemical. Within the facilities of ARI, a hot cell has been dedicated to this product and fitted out to manufacture it weekly on a cycle related to the operating cycle of the Australian reactor HIFAR. Due to neutron flux limitations of HIFAR, the local formulation has an elemental Samarium content up to 200μg/mL whereas the overseas formulation has a level of 20-46μg/mL. All other specifications of the two products are essentially the same. In 1995 and 1996 a small clinical trial with 19 patients was held which demonstrated that the pharmacokinetic behaviour was also essentially the same by measuring blood clearance rates and skeletal uptake dynamics. Soft tissue uptake was also qualitatively determined. The ARI version is now the subject of an application for general marketing within Australia. Some useful characteristics of this agent are: almost complete excretion or fixation in the skeleton within 6 hours, rapid onset of clinical effect, applicability in most cases where an abnormal diagnostic bone scan correlates with painful sites, dosage can be tailored to individual patient uptake due to easy dose measurement and retreatment is quite possible. The use of this class of agents in pain palliation continues to increase. Australian manufacture of Quadramet TM provides a further option in the management of these difficult cases

Production of SmCo5 alloy by calciothermic reduction of samarium oxide

International Nuclear Information System (INIS)

Krishnan, T.S.; Gupta, C.K.

1988-01-01

Among the established permanent magnets, SmCo 5 magnet occupies the foremost position as it offers a unique combination of high energy product, coercivity and curie temperature. The SmCo 5 magnets are thus extensively used for high field applications. These are also best suited for use in environments where high demagnetizing field and high temperature are operative. Also, for applications where high performance and miniaturization are the over-riding considerations, the choice again falls on SmCo 5 magnets. The main deterrent to the widespread use of SmCo 5 magnet is its high cost. Both samarium and cobalt metals are high priced, and the magnets prepared from their directly melted alloy are thus naturally very expensive. An alternate process involving calcium reduction of their oxide intermediates has, therefore, been studied and the alloy prepared by this process has been evaluated and found satisfactory for magnet production. The process essentially involves compaction of the charge mix containing samarium oxide, cobalt oxide (or metal) and calcium metal and reduction of the charge compact at 1000-1300 degrees C in hydrogen atmosphere, followed by water and acid leaching, drying and classification

Samarium oxide as a radiotracer to evaluate the in vivo biodistribution of PLGA nanoparticles

CSIR Research Space (South Africa)

Mandiwana, V

2015-09-01

Full Text Available the biodistribution of poly(D,L-lactide-co-glycolide) (PLGA) nanoparticles containing samarium-153 oxide ([(sup153)Sm]Sm(sub2)O(sub3)) in vivo to prove that orally administered nanoparticles alter the biodistribution of a drug. These were then activated in a nuclear...

Neutron Capture and Transmission Measurements and Resonance Parameter Analysis of Samarium

International Nuclear Information System (INIS)

Leinweber, G.; Burke, J.A.; Knox, H.D.; Drindak, N.J.; Mesh, D.W.; Haines, W.T.; Ballad, R.V.; Block, R.C.; Slovacek, R.E.; Werner, C.J.; Trbovich, M.J.; Barry, D.P.; Sato, T.

2001-01-01

The purpose of the present work is to accurately measure the neutron cross sections of samarium. The most significant isotope is 149 Sm, which has a large neutron absorption cross section at thermal energies and is a 235 U fission product with a 1% yield. Its cross sections are thus of concern to reactor neutronics. Neutron capture and transmission measurements were performed by the time-of-flight technique at the Rensselaer Polytechnic institute (RPI) LINAC facility using metallic and liquid Sm samples. The capture measurements were made at the 25 meter flight station with a multiplicity-type capture detector, and the transmission total cross-section measurements were performed at 15- and 25-meter flight stations with 6 Li glass scintillation detectors. Resonance parameters were determined by a combined analysis of six experiments (three capture and three transmission) using the multi-level R-matrix Bayesian code SAMMY version M2. The significant features of this work are as follows. Dilute samples of samarium nitrate in deuterated water (D 2 O) were prepared to measure the strong resonances at 0.1 and 8 eV without saturation. Disk-shaped spectroscopic quartz cells were obtained with parallel inner surfaces to provide a uniform thickness of solution. The diluent feature of the SAMMY program was used to analyze these data. The SAMMY program also includes multiple scattering corrections to capture yield data and resolution functions specific to the RPI facility. Resonance parameters for all stable isotopes of samarium were deduced for all resonances up to 30 eV. Thermal capture cross-section and capture resonance integral calculations were made using the resultant resonance parameters and were compared to results obtained using resonance parameters from ENDF/B-VI updated through release 3. Extending the definition of the capture resonance integral to include the strong 0.1 eV resonance in 149 Sm, present measurements agree within estimated uncertainties with En

Identification of the lines in the L emission spectrum of cerium and samarium

International Nuclear Information System (INIS)

Shrivastava, B.D.; Singh, D.

1992-01-01

The occurrence of a line at 2.1556 A in the L emission spectrum of cerium and two lines at 1.6679 and 1.8379 A in the L emission spectrum of samarium, reported many years ago, has remained a puzzle. These have now been identified as EXAFS minima occurring at the L absorption edges of the respective elements. (author)

Polymerase chain reaction-mediated DNA fingerprinting for epidemiological studies on Campylobacter spp

NARCIS (Netherlands)

Giesendorf, B A; Goossens, H; Niesters, H G; Van Belkum, A; Koeken, A; Endtz, H P; Stegeman, H; Quint, W G

The applicability of polymerase chain reaction (PCR)-mediated DNA typing, with primers complementary to dispersed repetitive DNA sequences and arbitrarily chosen DNA motifs, to study the epidemiology of campylobacter infection was evaluated. With a single PCR reaction and simple gel electrophoresis,

Samarium-153-EDTMP in the metastatic bone pain treatment

International Nuclear Information System (INIS)

Lins Filho, M.L.M.; Santos, A.O.; Nappi, A.P.B.; Meirelles, M.B.; Arouca, P.T.; Ramos, C.D.; Etchebehere, E.C.S.C.; Teixeira, L.C.; Netto Junior, N.R.; D'Ancona Cal; Camargo, E.E.

1997-01-01

Full text: Bone metastasis is the most reason of pain in prostate and mammary cancer patients. The Samarium-153-EDTMP has been showed as an alternative to the treatment of the metastasis bone pain. With the objective to evaluate the use of the Sm-153-EDTMP as a systemic therapy for the metastasis bone pain, 30 patients (19 male, 11 female, average age of 64,5 years) were studied. 19 patients with prostate cancer and 11 with mammary cancer. All the patients presented previous bone scintiscanning with multiple metastasis; interruption of the chemotherapy or radiotherapy for two or more weeks and leukocyte count higher than 2,000 leukocytes/mm 3 and platelets higher than 80,000/mm 3 . The patients were classified previously to the radioisotope therapy, as far the intensity of the pain in a scale from 0 to 10 is concerned. All the patients received 37 MBq/kg (1m Ci/kg) of weight of Sm-153-EDTMP by venous via. The evaluation 6 weeks after the therapy showed complete or partial pain relief in 22 patients (73,3%). Complete or partial pain relief has been obtained in 91,0% (10 in 11) of the patients with mammary cancer and in 62,2% (12 in 19) of the patients with prostate cancer. Transitory leukopenia (lower than 2,000 leukocytes/mm 3 ) and platelet count (lower than 80,000/mm 3 ) occurred in 33,3% of the patients. 8 patients (26,7%) did not responded to the therapy. The therapy with Samarium-153-EDTMP is a simple, safe and efficient method in the treatment of the bone pain caused by metastasis

Dependence of samarium-soil interaction on samarium concentration: Implications for environmental risk assessment.

Science.gov (United States)

Ramírez-Guinart, Oriol; Salaberria, Aitor; Vidal, Miquel; Rigol, Anna

2018-03-01

The sorption and desorption behaviour of samarium (Sm), an emerging contaminant, was examined in soil samples at varying Sm concentrations. The obtained sorption and desorption parameters revealed that soil possessed a high Sm retention capacity (sorption was higher than 99% and desorption lower than 2%) at low Sm concentrations, whereas at high Sm concentrations, the sorption-desorption behaviour varied among the soil samples tested. The fractionation of the Sm sorbed in soils, obtained by sequential extractions, allowed to suggest the soil properties (pH and organic matter solubility) and phases (organic matter, carbonates and clay minerals) governing the Sm-soil interaction. The sorption models constructed in the present work along with the sorption behaviour of Sm explained in terms of soil main characteristics will allow properly assessing the Sm-soil interaction depending on the contamination scenario under study. Moreover, the sorption and desorption K d values of radiosamarium in soils were strongly correlated with those of stable Sm at low concentrations (r = 0.98); indicating that the mobility of Sm radioisotopes and, thus, the risk of radioactive Sm contamination can be predicted using data from low concentrations of stable Sm. Copyright © 2017 Elsevier Ltd. All rights reserved.

Thermomechanical behavior of Fe-Mn-Si-Cr-Ni shape memory alloys modified with samarium

International Nuclear Information System (INIS)

Shakoor, R.A.; Khalid, F. Ahmad

2009-01-01

The deformation and training behavior of Fe-14Mn-3Si-10Cr-5Ni (wt.%) shape memory alloys containing samarium addition has been studied in the iron-based shape memory alloys. It is noticed that thermomechanical treatment (training) has significant influence on proof stress, critical stress and shape memory behavior of the alloys. The improvement in shape memory behavior can be attributed to the decrease in the proof stress and critical stress which facilitates the formation of ε (hcp martensite). It is also observed that alloy 2 containing samarium undergoes less softening as compared to alloy 1 with training which inhibits the formation of α (bcc martensite) and thus enhances the shape memory behavior. The excessive thermomechanical treatment with increase in the training cycle has led to the formation of α (bcc martensite) along with ε (hcp martensite) in the alloy 1 which appeared to have decline in the shape memory effect. This has been demonstrated by the examination of microstructure and identification of α (bcc martensite) martensite in the alloy 1 as compared to alloy 2

Effective visible light-active nitrogen and samarium co-doped BiVO4 for the degradation of organic pollutants

International Nuclear Information System (INIS)

Wang, Min; Niu, Chao; Liu, Jun; Wang, Qianwu; Yang, Changxiu; Zheng, Haoyan

2015-01-01

Nitrogen and samarium co-doped BiVO 4 (N–xSm–BiVO 4 ) nanoparticles were synthesized using a sol–gel method with a corn stem template. The physicochemical properties of the resultant N–xSm–BiVO 4 particles were characterized using various methods: XPS, XRD, SEM, BET, and UV–Vis DRS analyses. The visible-light photocatalytic activity was successfully demonstrated by degrading a model dye, namely, methyl orange. The dopant content was optimized, and the nitrogen and samarium co-doped BiVO 4 extended the light absorption spectrum toward the visible region, significantly enhancing the photodegradation of the model dye. The Sm and N co-doped BiVO 4 exhibited the highest photocatalytic activity compared to materials with a single dopant or no dopant. The significantly enhanced photocatalytic activity of the N–Sm co-doped BiVO 4 under visible-light irradiation can be attributed to the synergistic effects of the nitrogen and samarium. - Highlights: • The N–Sm codoped BiVO 4 were synthesized using a sol–gel method with a corn stem template. • The N and Sm codoped BiVO 4 has excellent photocatalytic activity of methyl orange degradation. • The maximum activity was observed when the molar ratio of Sm/Bi was 1.0. • The high photocatalytic activity was caused by the synergistic effects between N doping and Sm doping

Proanthocyanidin-rich Pinus radiata bark extract inhibits mast cell-mediated anaphylaxis-like reactions.

Science.gov (United States)

Choi, Yun Ho; Song, Chang Ho; Mun, Sung Phil

2018-02-01

Mast cells play a critical role in the effector phase of immediate hypersensitivity and allergic reactions. Pinus radiata bark extract exerts multiple biological effects and exhibits immunomodulatory and antioxidant properties. However, its role in mast cell-mediated anaphylactic reactions has not been thoroughly investigated. In this study, we examined the effects of proanthocyanidin-rich water extract (PAWE) isolated from P. radiata bark on compound 48/80-induced or antidinitrophenyl (DNP) immunoglobulin E (IgE)-mediated anaphylaxis-like reactions in vivo. In addition, we evaluated the mechanism underlying the inhibitory effect of PAWE on mast cell activation, with a specific focus on histamine release, using rat peritoneal mast cells. PAWE attenuated compound 48/80-induced or anti-DNP IgE-mediated passive cutaneous anaphylaxis-like reactions in mice, and it inhibited histamine release triggered by compound 48/80, ionophore A23187, or anti-DNP IgE in rat peritoneal mast cells in vitro. Moreover, PAWE suppressed compound 48/80-elicited calcium uptake in a concentration-dependent manner and promoted a transient increase in intracellular cyclic adenosine-3',5'-monophosphate levels. Together, these results suggest that proanthocyanidin-rich P. radiata bark extract effectively inhibits anaphylaxis-like reactions. Copyright © 2017 John Wiley & Sons, Ltd.

Controlling the photochemical reaction of an azastilbene derivative in water using a water-soluble pillar[6]arene.

Science.gov (United States)

Xia, Danyu; Wang, Pi; Shi, Bingbing

2017-09-20

Photochemistry plays an important role in our lives. It has also been a common tool in the laboratory to construct complicated systems from small molecules. Supramolecular chemistry provides an opportunity to solve some of the problems in controlling photochemical reactions via non-covalent interactions. By using confining media and weak interactions between the medium and the reactant molecule, the excited state behavior of molecules has been successfully manipulated. Pillararenes, a new class of macrocyclic hosts, have rarely been used in the field of photochemical investigations, such as the controlling of photo-induced reactions. Herein, we explore a synthetic macrocyclic host, a water-soluble pillar[6]arene, as a controlling tool to manipulate the photo-induced reactions (hydration) in water. A host-guest system in water based on a water-soluble pillar[6]arene and an azastilbene derivative, (E)-4,4'-dimethyl-4,4'-diazoniastilbene diiodide, has been constructed. Then this water-soluble pillar[6]arene was successfully employed to control the photohydration of the azastilbene derivative in water as a "protective agent".

Resonances of coherent population trapping in samarium vapours

International Nuclear Information System (INIS)

Kolachevsky, Nikolai N; Akimov, A V; Kiselev, N A; Papchenko, A A; Sorokin, Vadim N; Kanorskii, S I

2001-01-01

Resonances of coherent population trapping were detected in atomic vapours of the rare-earth element samarium. The coherent population trapping was produced by two external-cavity diode lasers (672 and 686 nm) in a Λ-system formed by the three levels of 154 Sm: the 4f 6 6s 2 ( 7 F 0 ) ground state, the first fine-structure 4f 6 6s 2 ( 7 F 1 ) sublevel of the ground state and the 4f 6 ( 7 F)6s6p( 3 P o ) 9 F o 1 upper level. The dependence of the spectral shapes and resonance contrasts on the polarisation of the laser beams and the direction of the applied magnetic field was studied. The obtained results were analysed. (nonlinear optical phenomena)

Journal of Chemical Sciences | Indian Academy of Sciences

Indian Academy of Sciences (India)

mercury(II)]2 complex · Tarlok S Lobana Amarjeet Singh Mandeep Kaur Alfonso Castineiras · More Details Abstract Fulltext PDF. Reaction of mercury(II) diiodide with triphenyl selenophosphorane-Se (1:1 mole ratio) in acetone followed by ...

Local cell-mediated immune reactions in cancer patients

International Nuclear Information System (INIS)

Bilynskij, B.T.; Vasil'ev, N.V.; Volod'ko, N.A.; Akademiya Meditsinskikh Nauk SSSR, Tomsk. Onkologicheskij Nauchnyj Tsentr)

1988-01-01

The analysis of 178 cases of stage I-II breast cancer showed morphological features of local cell-mediated immune reactions to be of limited prognostic value. A comparative evaluation of some characteristics of cell surface receptors, such as ability to spontaneous rosette formation with sheep erythrocytes and sensitivty to theophylline, was carried out in lymphocyte samples obtained from tumor tissue and peripheral blood of 76 cancer patients subjected to preoperative radiotherapy. The said parameters were studied in breast cancer patients of rosette-forming cell reaction to theophylline were identified, the incidence of some of them being determined by the presence or absence of regional metastases. The level and functional activity of surface receptors of tumor mononuclear cells proved to influence prognosis

The systems lanthanum (cerium, samarium) nitrate-tetramethyl-ammonium nitrate-water

International Nuclear Information System (INIS)

Zhuravlev, E.F.; Khisaeva, D.A.; Semenova, Eh.B.

1984-01-01

The method of cross sections at 25 and 50 deg C has been applied to study solubility in the systems lanthanum nitrate-tetramethyl ammonium nitrate-water (1), cesium (3) nitrate-tetramethyl ammonium nitrate-water (2) and samarium nitrate-tetramethyl ammonium nitrate-water (3). Crystallization fields of congruently dissolving compounds with 1:3 ratio of salt components (in system 1) and 1:2 ratio (in systems 2 and 3) are found in the systems. New solid phases are separated preparatively and subjected to chemical, differential thermal and IR spectroscopic analyses. Compositions of formed compounds are compared with the compositions known for nitrates of other representatives of light lanthanides

The systems cerium(3) (samarium) nitrate-quinoline nitrate-water

International Nuclear Information System (INIS)

Khisaeva, D.A.; Zhuravlev, E.F.; Semenova, Eh.B.

1982-01-01

Using the method of cross sections at 25 and 50 deg C the solubility in the systems cerium (3) nitrate-quinoline nitrate-water and samarium nitrate-quinoline nitrate-water has been studied. It is established that in the systems during chemical interaction of components congruently melting compounds of the composition: Ce(NO 3 ) 2 x2[C 9 H 7 NxHNO 3 ]x6H 2 O and Sm(NO 3 ) 3 x2[C 9 H 7 NxHNO 3 ]x2H 2 O are formed. New solid phases are separated preparatively and are subjected to chemical, differential thermal and IR spectroscopic analyses. The investigation results are compared with similar ones for nitrates of other representatives of lanthanide group

Body composition analysis by DEXA by using dynamically changing samarium filtration

DEFF Research Database (Denmark)

Gotfredsen, Arne; Baeksgaard, L; Hilsted, J

1997-01-01

Dual-energy X-ray absorptiometry (DEXA) has a high accuracy for body composition analysis but is influenced by beam hardening and other error sources in the extremes of measurement. To compensate for beam hardening, the Norland XR-36 introduces a dynamically changing samarium filtration system......). Scans of six healthy volunteers covered with combinations of beef and lard (approximately 5-15 kg) showed a good agreement (r = 0.99) between reference and DEXA values of added soft tissue mass and fat percentage. We conclude that the DEXA method (and, in particular, the Norland XR-36 using dynamic...

Solar Hydrogen Production via a Samarium Oxide-Based Thermochemical Water Splitting Cycle

Directory of Open Access Journals (Sweden)

Rahul Bhosale

2016-04-01

Full Text Available The computational thermodynamic analysis of a samarium oxide-based two-step solar thermochemical water splitting cycle is reported. The analysis is performed using HSC chemistry software and databases. The first (solar-based step drives the thermal reduction of Sm2O3 into Sm and O2. The second (non-solar step corresponds to the production of H2 via a water splitting reaction and the oxidation of Sm to Sm2O3. The equilibrium thermodynamic compositions related to the thermal reduction and water splitting steps are determined. The effect of oxygen partial pressure in the inert flushing gas on the thermal reduction temperature (TH is examined. An analysis based on the second law of thermodynamics is performed to determine the cycle efficiency (ηcycle and solar-to-fuel energy conversion efficiency (ηsolar−to−fuel attainable with and without heat recuperation. The results indicate that ηcycle and ηsolar−to−fuel both increase with decreasing TH, due to the reduction in oxygen partial pressure in the inert flushing gas. Furthermore, the recuperation of heat for the operation of the cycle significantly improves the solar reactor efficiency. For instance, in the case where TH = 2280 K, ηcycle = 24.4% and ηsolar−to−fuel = 29.5% (without heat recuperation, while ηcycle = 31.3% and ηsolar−to−fuel = 37.8% (with 40% heat recuperation.

Effective visible light-active nitrogen and samarium co-doped BiVO{sub 4} for the degradation of organic pollutants

Energy Technology Data Exchange (ETDEWEB)

Wang, Min; Niu, Chao [College of Environmental and Chemical Engineering, Shenyang Ligong University, Shenyang 110165 (China); Liu, Jun, E-mail: minwang62@msn.com [Shenyang Military General Hospital, Shenyang 110016 (China); Wang, Qianwu; Yang, Changxiu; Zheng, Haoyan [College of Environmental and Chemical Engineering, Shenyang Ligong University, Shenyang 110165 (China)

2015-11-05

Nitrogen and samarium co-doped BiVO{sub 4} (N–xSm–BiVO{sub 4}) nanoparticles were synthesized using a sol–gel method with a corn stem template. The physicochemical properties of the resultant N–xSm–BiVO{sub 4} particles were characterized using various methods: XPS, XRD, SEM, BET, and UV–Vis DRS analyses. The visible-light photocatalytic activity was successfully demonstrated by degrading a model dye, namely, methyl orange. The dopant content was optimized, and the nitrogen and samarium co-doped BiVO{sub 4} extended the light absorption spectrum toward the visible region, significantly enhancing the photodegradation of the model dye. The Sm and N co-doped BiVO{sub 4} exhibited the highest photocatalytic activity compared to materials with a single dopant or no dopant. The significantly enhanced photocatalytic activity of the N–Sm co-doped BiVO{sub 4} under visible-light irradiation can be attributed to the synergistic effects of the nitrogen and samarium. - Highlights: • The N–Sm codoped BiVO{sub 4} were synthesized using a sol–gel method with a corn stem template. • The N and Sm codoped BiVO{sub 4} has excellent photocatalytic activity of methyl orange degradation. • The maximum activity was observed when the molar ratio of Sm/Bi was 1.0. • The high photocatalytic activity was caused by the synergistic effects between N doping and Sm doping.

Ferrites Ni{sub 0,5}Zn{sub 0,5}Fe{sub 2}O{sub 4} doped with samarium: structural analysis, morphological and electromagnetic; Ferritas Ni{sub 0,5}Zn{sub 0,5}Fe{sub 2}O{sub 4} dopada com samario: analise estrutural, morfologica e eletromagnetica

Energy Technology Data Exchange (ETDEWEB)

Costa, A.C.F.M.; Diniz, A.P., E-mail: anacristina@dema.ufcg.edu.br [Universidade Federal de Campina Grande (UFCG), PB (Brazil). Unidade Academinca de Engenharia de Materiais; Viana, K.M.S. [Universidade Federal do Rio Grande do Norte (UFRN), Natal, PE (Brazil). Escola de Ciencias e Tecnologia; Cornejo, D.R. [Universidade de Sao Paulo (USP), SP (Brazil). Instituto de Fisica; Kiminami, R.H.G.A. [Universidade Federal de Sao Carlos (UFSCar), SP (Brazil). Departamento de Engenharia de Materiais

2010-07-01

This paper proposes to investigate the sintering at 1200 deg C/2h of Ni{sub 0.5}Zn{sub 0.5}Fe{sub 2-x}Sm{sub x}O{sub 4} ferrite doped with 0.05; 0.075 e 0.1 mol of Sm synthesized by combustion reaction to evaluate the performance materials as absorbers of electromagnetic radiation. The influence of the concentration of samarium on the structure, morphology and electromagnetic properties of ferrites was studied. The resulting samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), magnetic measurements and reflectivity measurements in the frequency range between 8-12 GHz. The results showed that increasing the concentration of samarium caused a decrease in particle size of the samples, encouraging, therefore, to obtain materials with better values of magnetization and reflectivity, allowing for use as absorbers in narrow-band frequency between 9-10 GHz. (author)

Tc1-mediated contact sensitivity reaction, its mechanism and regulation

Directory of Open Access Journals (Sweden)

Magdalena Zemelka-Wiącek

2014-07-01

Full Text Available The contact hypersensitivity reaction (CHS to haptens is a classic example of cell-mediated immune response. In the effector phase, two stages can be distinguished: an early component, that appears only 2 hours after subsequent contact with the hapten, and the late component that develops approximately 24 hours later which is mediated by TCRαβ+ cells. The effector lymphocytes may be CD4+ T helper 1 (Th1 cells or CD8+ T cytotoxic 1 (Tc1 cells, which depends on the employed hapten and/or mice strain. NKT lymphocytes play the crucial role in the CHS initiation, by supporting B1 cells in the antigen-specific IgM antibodies production. The development of an early component is essential for the recruitment of T effector (Teff cells to the side of hapten deposition and for the complete expansion of inflammatory reaction. The CHS reaction is under T regulatory (Treg cells control, both in the induction phase as well as in the effector phase. A new view of a negative regulation of the Tc1 mediated CHS response is based on the suppression induced by epicutaneous (EC application of protein antigen. The DNP-BSA skin application, on a gauze patch, leads to a state of immunosuppression. This maneuver results in rising the population of Treg cells with TCRαβ+CD4+CD25+Foxp3+ phenotype. The mechanism of suppression requires direct contact between Treg cells and Teff cells and the participation of CTLA-4 molecule is also necessary. The described method of evoking immune tolerance via EC immunization may contribute to elaborate a new method of allergic contact dermatitis therapy. This is because of its effectiveness, ease of induction and non-invasive protein antigen application.

Halogeno Aldol Reaction of Ethyl Vinyl Ketone and Aldehydes Mediated by Titanium Tetrachloride

Directory of Open Access Journals (Sweden)

Guigen Li

2000-12-01

Full Text Available A three-component halogeno aldol reaction has been developed by using titanium tetrachloride as the halogen source as well as the Lewis acid mediator. The dehydration and elimination of hydrogen chloride were inhibited by conducting the reaction at 0 °C in dichloromethane or at room temperature with a shortened reaction time. Seven examples were examined, giving good to high yields (61 - 92% and modest stereoselectivity (syn/anti: 2.2/1.0 - 8.4/1.0.

Determination of micro amounts of samarium and europium by analogue derivative spectrophotometry

International Nuclear Information System (INIS)

Ishii, H.; Satoh, K.

1982-01-01

Derivative spectrophotometry using the analogue differentiation circuit was applied to the determination of samarium and europium at ppm levels. By measuring the second or the fourth derivative spectra of the characteristic absorption bands of both the rare earth ions around 400 nm, they can be determined directly and selectively in the presence of large amounts of most other rare earths without any prior separation. Further, aptly selecting conditions for the measurement of the derivative spectra, the simultaneous determination of both the rare earth elements was feasible. The principle and the characteristics of analogue derivative spectrophotometry are also described. (orig.) [de

Metal–selenium interactions. Crystal structure of binuclear [( 1η-iodo ...

Indian Academy of Sciences (India)

Unknown

2Departmento de Quimica Inorganica, Facultade de Farmacia, Universidade de Santiago, 15706, Santiago, Spain e-mail: tarlok@angelfire.com. MS received 11 September 2000; revised 13 November 2000. Abstract. Reaction of mercury(II) diiodide with triphenyl selenophosphorane–Se. (1:1 mole ratio) in acetone followed ...

New reduced variant in gadolinium and samarium monoxide thin films

Energy Technology Data Exchange (ETDEWEB)

Bist, B M.S.; Kumar, J; Srivastava, O N [Banaras Hindu Univ. (India). Dept. of Physics

1977-01-01

A new reduced phase has been observed in the thin films of gadolinium and samarium monoxides. This phase results on imparting an annealing treatment to the monoxides and is formed as a result of the creation and ordering of vacancies in the oxygen sublattice. The new phase has been analysed to possess a rhombohedral unit cell with lattice parameters a/sub R/ = a/sub 0/ square root of (3/2) and c/sub R/ = a/sub 0/ square root of 3 (based on hexagonal axes, a/sub 0/ being the lattice parameter of the fundamental zinc blende type unit cell of the monoxide). Based on the proposed structure, the new phase can be assigned the solid state chemical formula RO/sub x/ where R = Gd, Sm and x = 0.66.

Enhanced electron-lattice coupling under uniaxial stress in layered double hydroxides intercalated with samarium complexes

International Nuclear Information System (INIS)

Park, Ta-Ryeong

2004-01-01

We have applied uniaxial stress to samarium complexes by intercalating them into the gallery of a layered material and by using a diamond-anvil cell at 28 K. Although uniaxial stress reduces symmetry and removes degeneracy, the overall number of photoluminescence (PL) peaks evidently decreased with the application of uniaxial stress. This contradictory observation is explained by an increased electron-lattice coupling strength under uniaxial stress. This behavior is also confirmed by time-resolved PL data.

Mediated priming in the lexical decision task : Evidence from event-related potentials and reaction time

NARCIS (Netherlands)

Chwilla, DJ; Kolk, HHJ; Mulder, G

Mediated priming (e.g., from LION to STRIPES vis TIGER) is predicted by spreading activation models hut only by some integration model. The goal of the present research was to localize mediated priming by assessing two-step priming effects on N400 and reaction times (RT). We propose that the N400

Phase Composition of Samarium Niobate and Tantalate Thin Films Prepared by Sol-Gel Method

Science.gov (United States)

Bruncková, H.; Medvecký, Ľ.; Múdra, E.; Kovalčiková, A.; Ďurišin, J.; Šebek, M.; Girman, V.

2017-12-01

Samarium niobate SmNbO4 (SNO) and tantalate SmTaO4 (STO) thin films ( 100 nm) were prepared by sol-gel/spin-coating process on alumina substrates with PZT interlayer and annealing at 1000°C. The precursors of films were synthesized using Nb or Ta tartrate complexes. The improvement of the crystallinity of monoclinic M'-SmTaO4 phase via heating was observed through the coexistence of small amounts of tetragonal T-SmTa7O19 phase in STO precursor at 1000°C. The XRD results of SNO and STO films confirmed monoclinic M-SmNbO4 and M'-SmTaO4 phases, respectively, with traces of orthorhombic O-SmNbO4 (in SNO). In STO film, the single monoclinic M'-SmTaO4 phase was revealed. The surface morphology and topography of thin films were investigated by SEM and AFM analysis. STO film was smoother with roughness 3.2 nm in comparison with SNO (6.3 nm). In the microstructure of SNO film, small spherical ( 50 nm) and larger cuboidal particles ( 100 nm) of the SmNbO4 phase were observed. In STO, compact clusters composed of fine spherical SmTaO4 particles ( 20-50 nm) were found. Effect of samarium can contribute to the formation different polymorphs of these films for the application to environmental electrolytic thin film devices.

Combined effect of x irradiation and cell-mediated immune reaction

International Nuclear Information System (INIS)

Song, C.W.; Guertin, D.P.

1978-01-01

The combined effect of radiation and cell-mediated immune reaction on tumor cells was investigated in vitro. Mastocytoma P815-X2 cells of DBA mice either were irradiated first and subjected to immune lysis by immune splenic lymphocytes of C57Bl mice, or the tumor cells were subjected to immune reaction first and then irradiated. Cell survival was quantitated by colony formation in soft agar medium. It was observed that cellular immune damage to tumor cells did not influence the response of tumor cells to subsequent radiation. Irradiation of tumor cells first, followed by subjection of the cells to cellular immune reaction, slightly enhanced the death of the tumor cells. It appears that this enhanced death might have resulted from a relative increase in the ratio of the number of cytotoxic immune cells to the number of target tumor cells in the incubation mixture as a consequence of the decrease in the number of viable tumor cells by radiation

Evaluation of samarium-153 and holmium-166-EDTMP in the normal baboon model

Energy Technology Data Exchange (ETDEWEB)

Louw, W.K.A.; Dormehl, I.C.; Rensburg, A.J. van; Hugo, N.; Alberts, A.S.; Forsyth, O.E.; Beverley, G.; Sweetlove, M.A.; Marais, J.; Loetter, M.G.; Aswegen, A. van

1996-11-01

Bone-seeking radiopharmaceuticals such as ethylenediaminetetramethylene phosphonate (EDTMP) complexes of samarium-153 and holmium-166 are receiving considerable attention for therapeutic treatment of bone metastases. In this study, using the baboon experimental model, multicompartmental analysis revealed that with regard to pharmacokinetics, biodistribution, and skeletal localisation, {sup 166}Ho-EDTMP was significantly inferior to {sup 153}Sm-EDTMP and {sup 99m}Tc-MDP. A more suitable {sup 166}Ho-bone-seeking agent should thus be sought for closer similarity to {sup 153}Sm-EDTMP to exploit fully the therapeutic potential of its shorter half-life and more energetic beta radiation.

Performance analysis of samarium cobalt P.M. synchronous motor fed from PWM inverters

International Nuclear Information System (INIS)

Rahman, M.A.; Choudhury, M.A.

1985-01-01

This paper presents an analysis and performance of samarium cobalt permanent magnet (P.M.) synchronous motors fed from two types of voltage source pulse width modulated (PWM) inverters. The analysis and test results on the steady state performance of a P.M. motor fed from PWM inverters are presented. PWM inverters are used in variable voltage variable frequency applications to avoid a double conversion process of ordinary inverters. In drives, they are used for voltage and speed regulation of motors. Use of modulation technique in inverters also allow to eliminate or minimize selected harmonics from the inverter output voltage

JAEA thermodynamic database for performance assessment of geological disposal of high-level and TRU wastes. Refinement of thermodynamic data for trivalent actinoids and samarium

International Nuclear Information System (INIS)

Kitamura, Akira; Fujiwara, Kenso; Yui, Mikazu

2010-01-01

Within the scope of the JAEA thermodynamic database project for performance assessment of geological disposal of high-level radioactive and TRU wastes, the refinement of the thermodynamic data for the inorganic compounds and complexes of trivalent actinoids (actinium(III), plutonium(III), americium(III) and curium(III)) and samarium(III) was carried out. Refinement of thermodynamic data for these elements was based on the thermodynamic database for americium published by the Nuclear Energy Agency in the Organisation for Economic Co-operation and Development (OECD/NEA). Based on the similarity of chemical properties among trivalent actinoids and samarium, complementary thermodynamic data for their species expected under the geological disposal conditions were selected to complete the thermodynamic data set for the performance assessment of geological disposal of radioactive wastes. (author)

Retention capacity of samarium (III) in zircon for it possible use in retaining walls for confinement of nuclear residues

International Nuclear Information System (INIS)

Garcia G, N.

2006-01-01

Mexico, as country that produces part of its electric power by nuclear means, should put special emphasis in the development of technologies guided to the sure and long term confinement of the high level nuclear residuals. This work studies the capacity that has the natural zircon to retain to the samarium (III) in solution, by what due, firstly, to characterize the zircon for technical instrumental to determine the purity and characteristic of the mineral in study. The instrumental techniques that were used to carry out the physicochemical characterization were the neutron activation analysis (NAA), the infrared spectroscopy (IS), the thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), semiquantitative analysis, dispersive energy spectroscopy (EDS), X-ray diffraction (XRD) and luminescence technique. The characterization of the surface properties carries out by means of the determination of the surface area using the BET multipoint technique, acidity constants, hydration time, the determination of the point of null charge (pH PCN ) and density of surface sites (D s ). The luminescence techniques were useful to determine the optimal point hydration of the zircon and for the quantification of the samarium, for that here intends the development of both analysis techniques. With the adjustment of the titration curves in the FITEQL 4 package the constants of surface acidity in the solid/liquid interface were determined. To the finish of this study it was corroborated that the zircon is a mineral that presents appropriate characteristics to be proposed as a contention barrier for the deep geologic confinement. With regard to the study of adsorption that one carries out the samarium retention it is superior to 90% under the described conditions. This investigation could also be applicable in the confinement of dangerous industrial residuals. (Author)

Reclassifying Anaphylaxis to Neuromuscular Blocking Agents Based on the Presumed Patho-Mechanism: IgE-Mediated, Pharmacological Adverse Reaction or “Innate Hypersensitivity”?

Directory of Open Access Journals (Sweden)

David Spoerl

2017-06-01

Full Text Available Approximately 60% of perioperative anaphylactic reactions are thought to be immunoglobulin IgE mediated, whereas 40% are thought to be non-IgE mediated hypersensitivity reactions (both considered non-dose-related type B adverse drug reactions. In both cases, symptoms are elicited by mast cell degranulation. Also, pharmacological reactions to drugs (type A, dose-related may sometimes mimic symptoms triggered by mast cell degranulation. In case of hypotension, bronchospasm, or urticarial rash due to mast cell degranulation, identification of the responsible mechanism is complicated. However, determination of the type of the underlying adverse drug reaction is of paramount interest for the decision of whether the culprit drug may be re-administered. Neuromuscular blocking agents (NMBA are among the most frequent cause of perioperative anaphylaxis. Recently, it has been shown that NMBA may activate mast cells independently from IgE antibodies via the human Mas-related G-protein-coupled receptor member X2 (MRGPRX2. In light of this new insight into the patho-mechanism of pseudo-allergic adverse drug reactions, in which as drug-receptor interaction results in anaphylaxis like symptoms, we critically reviewed the literature on NMBA-induced perioperative anaphylaxis. We challenge the dogma that NMBA mainly cause IgE-mediated anaphylaxis via an IgE-mediated mechanism, which is based on studies that consider positive skin test to be specific for IgE-mediated hypersensitivity. Finally, we discuss the question whether MRGPRX2 mediated pseudo-allergic reactions should be re-classified as type A adverse reactions.

Optical properties and electronic transitions of zinc oxide, ferric oxide, cerium oxide, and samarium oxide in the ultraviolet and extreme ultraviolet

DEFF Research Database (Denmark)

Pauly, N; Yubero, F; Espinós, J P

2017-01-01

Optical properties and electronic transitions of four oxides, namely zinc oxide, ferric oxide, cerium oxide, and samarium oxide, are determined in the ultraviolet and extreme ultraviolet by reflection electron energy loss spectroscopy using primary electron energies in the range 0.3-2.0 ke...

Magnetic behavior study of samarium nitride using density functional theory

Science.gov (United States)

Som, Narayan N.; Mankad, Venu H.; Dabhi, Shweta D.; Patel, Anjali; Jha, Prafulla K.

2018-02-01

In this work, the state-of-art density functional theory is employed to study the structural, electronic and magnetic properties of samarium nitride (SmN). We have performed calculation for both ferromagnetic and antiferromagnetic states in rock-salt phase. The calculated results of optimized lattice parameter and magnetic moment agree well with the available experimental and theoretical values. From energy band diagram and electronic density of states, we observe a half-metallic behaviour in FM phase of rock salt SmN in while metallicity in AFM I and AFM III phases. We present and discuss our current understanding of the possible half-metallicity together with the magnetic ordering in SmN. The calculated phonon dispersion curves shows dynamical stability of the considered structures. The phonon density of states and Eliashberg functional have also been analysed to understand the superconductivity in SmN.

Myelotoxicity of Samarium Sm153 lexidronam in patients with painful bony metastases

International Nuclear Information System (INIS)

Ben Ghachem, T.; Mhiri, A.; Slim, I.; Bahloul, A.; Yeddes, I.; Elbez, I.; Meddeb, I.; Ben Slimene, M.F.

2015-01-01

Full text of publication follows. Introduction: the management of bone pain includes analgesia, radiation, hormones, radiofrequency (RF) ablation, chemotherapy, and surgery. Bone pain palliation therapy with radiopharmaceuticals is a cost-effective systemic therapy to relieve pain from skeletal metastases with a consequent decrease in morbidity and an improvement in quality of life. The aim of our study is to evaluate the effect of myelotoxicity of samarium lexidronam (Sm 153 ) in patients with painful bony metastasis. Methods: we reviewed 116 patients aged from 14 to 87 years old, 91 males (78%) and 25 females (22%), having received 1 to 4 treatments of Sm 153 (37 MBq/kg) for painful bony metastases from different primitive tumors: 67 cases of prostate cancer (57.7%), 22 cases of breast cancer (18.9%), 10 cases of pulmonary cancer (8.6%) and others in 14.6% of cases. Clinical follow-up was available for 159 treatments, consisting on blood count each week over at least two months, in order to evaluate myelotoxicity according to WHO classification. Results: no patients had grade 4 toxicity after its cures. A grade 2-3 myelotoxicity was observed after 52 treatments (34%) during the second week and after 50 treatments (32.6%) during the fourth week with a satisfactory reversibility. At 10 weeks of treatment, myelotoxicity was reclassified from 0 to 2 for 139 cures (90,8%). Moreover, we found that prior treatment with radiotherapy or chemotherapy did not affect the rates of myelotoxicity. Conclusion: multiple treatments with samarium Sm 153 lexidronam had no significant effect on myelotoxicity. Patients with bone predominant metastatic disease may survive for extended periods of time and may safely be treated with multiple modalities of therapy. (authors)

Engaging unactivated alkyl, alkenyl and aryl iodides in visible-light-mediated free radical reactions

Science.gov (United States)

Nguyen, John D.; D'Amato, Erica M.; Narayanam, Jagan M. R.; Stephenson, Corey R. J.

2012-10-01

Radical reactions are a powerful class of chemical transformations. However, the formation of radical species to initiate these reactions has often required the use of stoichiometric amounts of toxic reagents, such as tributyltin hydride. Recently, the use of visible-light-mediated photoredox catalysis to generate radical species has become popular, but the scope of these radical precursors has been limited. Here, we describe the identification of reaction conditions under which photocatalysts such as fac-Ir(ppy)3 can be utilized to form radicals from unactivated alkyl, alkenyl and aryl iodides. The generated radicals undergo reduction via hydrogen atom abstraction or reductive cyclization. The reaction protocol utilizes only inexpensive reagents, occurs under mild reaction conditions, and shows exceptional functional group tolerance. Reaction efficiency is maintained upon scale-up and decreased catalyst loading, and the reaction time can be significantly shortened when the reaction is performed in a flow reactor.

Study of unstable valences of cadmium and samarium by pulse radiolysis. Influence of complexation by some synthetical ionophores

International Nuclear Information System (INIS)

Lerat-Parizot, O.

1992-01-01

Instable valences of cations in solution are evidenced by pulse radiolysis, in spite of a lifetime often lower than a milli-second they participate to electron transfer reactions, owing to their redox potential. In this work are studied Cd + and Sm 2+ obtained respectively by reduction of Cd 2+ and Sm 3+ by a solvated electron. The reactivity of Cd + in a cryptand and in a coronand is studied; it is a powerful reducing agent (redox potential -2V) going back to the stable valence by electron transfer to an acceptor. Transfer kinetics is studied by reduction of organic molecules, effect of solvents and ligands is also examined. For samarium the reduction kinetics by hydrated electrons is increased when the ion is in a cryptand in agreement with electrochemical observations, showing that the valence 2+ is stabilized in respect to the valence 3+ for lanthanides. The difference of behaviour between Cd + and Sm 2+ is probably due to the fact that for Cd the transferred electron comes from the external layer and for Sm it is a f electron protected by the 5s and 5p orbitals

Fabrication of a PVC membrane samarium(III) sensor based on N,N′,N″-tris(4-pyridyl)trimesic amide as a selectophore

International Nuclear Information System (INIS)

Zamani, Hassan Ali; Naghavi-Reyabbi, Fatemeh; Faridbod, Farnoush; Mohammadhosseini, Majid; Ganjali, Mohammad Reza; Tadjarodi, Azadeh; Rad, Maryam

2013-01-01

A new ion-selective electrode for Sm 3+ ion is described based on the incorporation of N,N′,N″-tris(4-pyridyl)trimesic amide (TPTA) in a poly(vinylchloride) (PVC) matrix. The membrane sensor comprises nitrobenzene (NB) as a plasticizer, and oleic acid (OA) as an anionic additive. The sensor with the optimized composition shows a Nernstian potential response of 19.8 ± 0.5 mV decade −1 over a wide concentration range of 1.0 × 10 −2 and 1 × 10 −6 mol L −1 , with a lower detection limit of 4.7 × 10 −7 mol L −1 and satisfactor applicable pH range of 3.6–9.2. Having a short response time of less than 10 s and a very good selectivity towards the Sm 3+ over a wide variety of interfering cations (e.g. alkali, alkaline earth, transition and heavy metal ions) the sensor seemed to be a promising analytical tool for determination of the Sm 3+ . Hence, it was used as an indicator electrode in the potentiometric titration of samarium ion with EDTA. It was also applied to the direct samarium recovery in binary mixtures. - Highlights: ► A new Sm 3+ -PVC membrane sensor is introduced for determination of Sm 3+ ions in the solutions. ► N,N′,N″-tris(4-pyridyl)trimesic amide was used as a suitable selectophore for samarium sensor. ► Detection limit of the sensor is 4.7 × 10 −7 mol L −1 with a short response time of less than 10 s.

Optical and physical properties of samarium doped lithium diborate glasses

Science.gov (United States)

Hanumantharaju, N.; Sardarpasha, K. R.; Gowda, V. C. Veeranna

2018-05-01

Sm3+ doped lithium di-borate glasses with composition 30Li2O-60B2O3-(10-x) PbO, (where 0 molar volume with samarium ion content indicates the openness of the glass structure. The gradual increase in average separation of boron-boron atoms with VmB clearly indicates deterioration of borate glass network, which in turn leads to decrease in the oxygen packing density. The replacements of Sm2O3 for PbO depolymerise the chain structure and that would increase the concentration of non-bridging oxygens. The marginal increase of optical band gap energy after 1.0 mol.% of Sm2O3 is explained by considering the structural modification in lead-borate. The influence of Sm3+ ion on physical and optical properties in lithium-lead-borate glasses is investigated and the results were discussed in view of the structure of borate glass network.

Preparation and examination of properties of samarium-153-EDTMP complex; Otrzymywanie chelatu kwasu etylenodiaminotetrametylenofosfonowego (EDTMP) z samarem-153 i badanie jego wlasciwosci

Energy Technology Data Exchange (ETDEWEB)

Nowak, M. [Institute of Atomic Energy, Otwock-Swierk (Poland); Garnuszek, P.; Lukasiewicz, A.; Wozniak, I.; Zulczyk, W. [Osrodek Badawczo-Rozwojowy Izotopow, Otwock-Swierk (Poland); Licinska, I. [Instytut Lekow, Warsaw (Poland)

1995-12-31

Preparation and properties of ethylenediaminetetramethylenephosphonic acid (EDTMP) as well as some properties of {sup 153}Sm-EDTMP chelate have been examined. The chelate formed by samarium-153 (46.3 h, {beta}{sup -}-decay) with EDTMP exhibits high bone uptake and can be used for treatment of disseminated, painful skeletal metastases. The purity and stability of solutions of {sup 153}Sm-EDTMP chelate were examined in a broad range of samarium concentration and {sup 153}Sm specific activity. The complex under study was examined by radio-TLC, -electrophoresis and radio-HPLC. The results obtained suggest the small size of molecules of {sup 153}Sm-EDTMP chelate as compared with molecules of ``free``EDTMP. The results of biodistribution of {sup 153}Sm-EDTMP determined in rats indicate the quick blood clearance, high deposition of radioactivity in bone and quick excretion of radioactivity into urine. No specific uptake of {sup 153}Sm-EDTMP in extra-skeletal organs was found. (author). 42 refs, 13 figs, 22 tabs.

Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds

Directory of Open Access Journals (Sweden)

Burkhard Koenig

2011-01-01

Full Text Available N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald–Hartwig-type reactions, copper-mediated Ullmann-type and Chan–Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan–Lam reactions. Chan–Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald–Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C–N bond formation in the course of a total synthesis or drug synthesis.

Origin of Power Laws for Reactions at Metal Surfaces Mediated by Hot Electrons

DEFF Research Database (Denmark)

Olsen, Thomas; Schiøtz, Jakob

2009-01-01

A wide range of experiments have established that certain chemical reactions at metal surfaces can be driven by multiple hot-electron-mediated excitations of adsorbates. A high transient density of hot electrons is obtained by means of femtosecond laser pulses and a characteristic feature of such...... density functional theory and the delta self-consistent field method. With a simplifying assumption, the power law becomes exact and we obtain a simple physical interpretation of the exponent n, which represents the number of adsorbate vibrational states participating in the reaction....

Protective effect of chlorpromazine on TNF-mediated hapten-induced irritant reaction.

Science.gov (United States)

Erroi, A; Fantuzzi, G; Demitri, M T; Echtenacher, B; Gnocchi, P; Isetta, A; Ghezzi, P

1995-01-01

Picryl chloride-induced irritant reaction (IR) was shown to be mediated by tumor necrosis factor (TNF). Anti-TNF monoclonal antibodies, but not interleukin 1 receptor antagonist (IL-1 Ra), had a protective effect. Chlorpromazine (CPZ), an inhibitor of TNF synthesis, protected against IR and inhibited the IR-associated TNF induction in ear homogenates. Investigation of the role of polymorphonuclear leukocyte (PMN) in neutropenic mice showed that neutropenia did not prevent the development of the IR.

Structural phase transition and electronic properties in samarium chalcogenides

Energy Technology Data Exchange (ETDEWEB)

Panwar, Y. S., E-mail: yspanwar2011@gmail.com [Department of Physics, Govt. New Science College Dewas-455001 (India); Aynyas, Mahendra [Department of Physics, C.S.A. Govt. P.G. College, Sehore, 466001 (India); Pataiya, J.; Sanyal, Sankar P. [Department of Physics, Barkatullah University, Bhopal, 462026 (India)

2016-05-06

The electronic structure and high pressure properties of samarium monochalcogenides SmS, SmSe and SmTe have been reported by using tight binding linear muffin-tin-orbital (TB-LMTO) method within the local density approximation (LDA). The total energy as a function of volume is evaluated. It is found that these monochalcogenides are stable in NaCl-type structure under ambient pressure. We predict a structural phase transition from NaCl-type (B{sub 1}-phase) structure to CsCl-type (B{sub 2}-type) structure for these compounds. Phase transition pressures were found to be 1.7, 4.4 and 6.6 GPa, for SmS, SmSe and SmTe respectively. Apart from this, the lattice parameter (a{sub 0}), bulk modulus (B{sub 0}), band structure (BS) and density of states (DOS) are calculated. From energy band diagram we observed that these compounds exhibit metallic character. The calculated values of equilibrium lattice parameter and phase transition pressure are in general good agreement with available data.

Radical-mediated annulation reactions. A versatile strategy for the preparation of a series of carbocycles.

Science.gov (United States)

Sibi, M P; Chen, J; Rheault, T R

2001-11-15

[reaction--see text] A series of novel 6-endo [4 + 2] and 7-endo [5 + 2] radical-mediated annulation reactions are described. These annulation sequences involve an intermolecular radical addition followed by intramolecular trapping with an allyltin moiety incorporated into the radical precursor fragment. This methodology allows for access to functionalized 6- and 7-membered carbocycles as well as bicyclic compounds with good to excellent levels of stereocontrol.

Effect of seven Indian plant extracts on Fenton reaction-mediated damage to DNA constituents.

Science.gov (United States)

Kar, Indrani; Chattopadhyaya, Rajagopal

2017-11-01

The influences of substoichiometric amounts of seven plant extracts in the Fenton reaction-mediated damage to deoxynucleosides, deoxynucleoside monophosphates, deoxynucleoside triphosphates, and supercoiled plasmid DNA were studied to rationalize anticancer properties reported in some of these extracts. Extracts from Acacia catechu, Emblica officinalis, Spondias dulcis, Terminalia belerica, Terminalia chebula, as well as gallic acid, epicatechin, chebulagic acid and chebulinic acid enhance the extent of damage in Fenton reactions with all monomeric substrates but protect supercoiled plasmid DNA, compared to standard Fenton reactions. The damage to pyrimidine nucleosides/nucleotides is enhanced by these extracts and compounds to a greater extent than for purine ones in a concentration dependent manner. Dolichos biflorus and Hemidesmus indicus extracts generally do not show this enhancement for the monomeric substrates though they protect plasmid DNA. Compared to standard Fenton reactions for deoxynucleosides with ethanol, the presence of these five plant extracts render ethanol scavenging less effective as the radical is generated in the vicinity of the target. Since substoichiometric amounts of these extracts and the four compounds produce this effect, a catalytic mechanism involving the presence of a ternary complex of the nucleoside/nucleotide substrate, a plant compound and the hydroxyl radical is proposed. Such a mechanism cannot operate for plasmid DNA as the planar rings in the extract compounds cannot stack with the duplex DNA bases. These plant extracts, by enhancing Fenton reaction-mediated damage to deoxynucleoside triphosphates, slow down DNA replication in rapidly dividing cancer cells, thus contributing to their anticancer properties.

Sorption of samarium in iron (II) and (III) phosphates in aqueous systems; Sorcion de samario en fosfatos de hierro (II) y (III) en sistemas acuosos

Energy Technology Data Exchange (ETDEWEB)

Diaz F, J C

2006-07-01

The radioactive residues that are stored in the radioactive confinements its need to stay isolated of the environment while the radioactivity levels be noxious. An important mechanism by which the radioactive residues can to reach the environment, it is the migration of these through the underground water. That it makes necessary the investigation of reactive materials that interacting with those radionuclides and that its are able to remove them from the watery resources. The synthesis and characterization of materials that can be useful in Environmental Chemistry are very important because its characteristics are exposed and its behavior in chemical phenomena as the sorption watery medium is necessary to use it in the environmental protection. In this work it was carried out the sorption study of the samarium III ion in the iron (II) and (III) phosphate; obtaining the sorption isotherms in function of pH, of the phosphate mass and of the concentration of the samarium ion using UV-visible spectroscopy to determine the removal percentage. The developed experiments show that as much the ferrous phosphate as the ferric phosphate present a great affinity by the samarium III, for what it use like reactive material in contention walls can be very viable because it sorption capacity has overcome 90% to pH values similar to those of the underground and also mentioning that the form to obtain these materials is very economic and simple. (Author)

Studies on the rare earth complexes with pyridine derivatives and their N-oxide(II) - Synthesis and properties of fluorescent solid complexes of samarium, europium, gadolium and terbium chlorides with 2,2'-bipyridine-N,N'-dioxide

International Nuclear Information System (INIS)

Minyu, T.; Ning, T.; Yingli, Z.; Jiyuan, B.

1985-01-01

The solid complexes of rare earth nitrates perchlorates and thiocyanates with 2,2'-bipyridine-N,N'-dioxide (bipyO/sub 2/) have been reported. However, the corresponding complexes of other rear earth chlorides have not been investigated except lanthanum, cerium and yttrium. As an extension of our previous work on the synthesis of complexes of praseodymium and neodymium chlorides wiht bipoyO/sub 2/, the authors have now prepared fluorescent solid complexes of samarium, europium, gadolium and terbium chlorides with biphyO/sub 2/, using methanol as a reaction medium. The new synthesized compounds have been identified by means of elemental analysis, infrared spectrometry, conductometry, differential thermal analysis (DTA), thermogravimetry (TG) and X-ray powder diffraction

Randomized, controlled trial of TNF-α antagonist in CTL-mediated severe cutaneous adverse reactions.

Science.gov (United States)

Wang, Chuang-Wei; Yang, Lan-Yan; Chen, Chun-Bing; Ho, Hsin-Chun; Hung, Shuen-Iu; Yang, Chih-Hsun; Chang, Chee-Jen; Su, Shih-Chi; Hui, Rosaline Chung-Yee; Chin, See-Wen; Huang, Li-Fang; Lin, Yang Yu-Wei; Chang, Wei-Yang; Fan, Wen-Lang; Yang, Chin-Yi; Ho, Ji-Chen; Chang, Ya-Ching; Lu, Chun-Wei; Chung, Wen-Hung

2018-03-01

Cytotoxic T lymphocyte-mediated (CTL-mediated) severe cutaneous adverse reactions (SCARs), including Stevens-Johnson syndrome (SJS) and toxic epidermal necrolysis (TEN), are rare but life-threatening adverse reactions commonly induced by drugs. Although high levels of CTL-associated cytokines, chemokines, or cytotoxic proteins, including TNF-α and granulysin, were observed in SJS-TEN patients in recent studies, the optimal treatment for these diseases remains controversial. We aimed to evaluate the efficacy, safety, and therapeutic mechanism of a TNF-α antagonist in CTL-mediated SCARs. We enrolled 96 patients with SJS-TEN in a randomized trial to compare the effects of the TNF-α antagonist etanercept versus traditional corticosteroids. Etanercept improved clinical outcomes in patients with SJS-TEN. Etanercept decreased the SCORTEN-based predicted mortality rate (predicted and observed rates, 17.7% and 8.3%, respectively). Compared with corticosteroids, etanercept further reduced the skin-healing time in moderate-to-severe SJS-TEN patients (median time for skin healing was 14 and 19 days for etanercept and corticosteroids, respectively; P = 0.010), with a lower incidence of gastrointestinal hemorrhage in all SJS-TEN patients (2.6% for etanercept and 18.2% for corticosteroids; P = 0.03). In the therapeutic mechanism study, etanercept decreased the TNF-α and granulysin secretions in blister fluids and plasma (45.7%-62.5% decrease after treatment; all P etanercept serves as an effective alternative for the treatment of CTL-mediated SCARs. ClinicalTrials.gov NCT01276314. Ministry of Science and Technology of Taiwan.

Separation of lanthanum from samarium on solid aluminum electrode in LiCl-KCl eutectic melts

International Nuclear Information System (INIS)

De-Bin Ji; Mi-Lin Zhang; Xing Li; Xiao-Yan Jing; Wei Han; Yong-De Yan; Yun Xue; Zhi-Jian Zhang; Harbin Engineering University, Harbin

2015-01-01

This paper presents an electrochemical study on the separation of lanthanum from samarium on aluminum electrode at 773 K. The results from different electrochemical methods showed that Sm(III) and La(III) formed Al-Sm and Al-La intermetallic compounds on an aluminum electrode at electrode potential around -1.67 and -1.46 V, respectively. The electrochemical separation of lanthanum was carried out in LiCl-KCl-LaCl 3 -SmCl 3 melts on solid aluminum electrodes at 773 K by potentiostatic electrolysis at -1.45 V for 40 h and the separation efficiency was 99.1 %. (author)

Structural and luminescence properties of samarium doped lead alumino borate glasses

Science.gov (United States)

Mohan, Shaweta; Kaur, Simranpreet; Singh, D. P.; Kaur, Puneet

2017-11-01

The study reports the effect of samarium concentration on the physical, structural and spectroscopic characteristics of samarium doped lead alumino borate glasses having composition 20PbO-(10-x)Al2O3-70B2O3-xSm2O3; x = 0.1, 0.5, 1.0 and 2.0 mol %. The glasses were fabricated by conventional melt-quenching technique and then characterized by XRD, FTIR, optical absorption and fluorescence spectra. X-ray diffraction studies confirmed the amorphous nature of the prepared glasses. FTIR spectra indicate the presence of BO3, BO4, AlO6 and a few other structural groups. Various physical properties such as density, molar volume, refractive index, rare earth ion concentration, boron-boron distance and polarizability etc. were determined using conventional methods and standard formulae. The Judd-Ofelt theory was applied on the optical absorption spectra of the glasses to evaluate the three phenomenological intensity parameters Ω2, Ω4 and Ω6. The value of Ω2 was found to be highest for glass with 1 mol% Sm2O3 and attributed to the asymmetry of the ligand field at the rare earth ion site and the rare earth oxygen (Sm-O) covalency. The calculated intensity parameters and fluorescence spectra were further used to predict the radiative transition probability (A), radiative lifetime (τR), branching ratio (βR), peak wavelength (λp), effective line widths (Δλeff) and stimulated emission cross-section (σ) for the characteristic 4G5/2 → 6H5/2, 6H7/2 and 6H9/2 transitions of the Sm3+ ion. Concentration quenching was observed for 2 mol% concentration of Sm2O3 and ascribed to energy transfer through various cross-relaxation channels between Sm3+ ions. Reasonably high values of branching ratios and stimulated emission cross-section for the prepared glasses points towards their utility in the development of visible lasers emitting in the reddish-orange spectral region. However, the glass with 1 mol% Sm2O3 was found to show better radiative properties.

On the length dependence of bridge-mediated electron transfer reactions

International Nuclear Information System (INIS)

Petrov, E.G.; Shevchenko, Ye.V.; May, V.

2003-01-01

Bridge-mediated nonadiabatic donor-acceptor (D-A) electron transfer (ET) is studied for the case of a regular molecular bridge of N identical units. It is shown that the multi-exponential ET kinetics reduces to a single-exponential transfer if, and only if, the integral population of the bridge remains small (less than 10 -2 ). An analytical expression for the overall D-A ET rate is derived and the necessary and sufficient conditions are formulated at which the rate is given as a sum of a superexchange and a sequential contribution. To describe experimental data on the N-dependence of ET reactions an approximate form of the overall transfer rate is derived. This expression is used to reproduce experimental data on distant ET through polyproline chains. Finally it is noted that the obtained analytical results can also be used for the description of more complex two-electron transfer reactions if the latter comprises separate single-electron pathways

Europium and samarium doped calcium sulfide thin films grown by PLD

International Nuclear Information System (INIS)

Christoulakis, S.; Suchea, M; Katsarakis, N.; Koudoumas, E

2007-01-01

Europium and samarium doped calcium sulfide thin films (CaS:Eu,Sm) with different thickness were prepared by the pulsed laser deposition technique using sintered targets. A typical homemade deposition chamber and XeCl excimer laser (308 nm) were employed and the films were deposited in helium atmosphere onto silicon and corning glass substrates. Structural investigations carried out by X-ray diffraction and atomic force microscopy showed a strong influence of the deposition parameters on the film properties. The films grown had an amorphous or polycrystalline structure depending on growth temperature and the number of pulses used, the same parameters affecting the film roughness, the grain shape and dimensions, the film thickness and the optical transmittance. This work indicates that pulsed laser deposition can be a suitable technique for the preparation of CaS:Eu,Sm thin films, the film characteristics being controlled by the growth conditions

Synthesis and reactivity of 10-alkylphenotellurazines

International Nuclear Information System (INIS)

Sadekov, I.D.; Abakarov, G.M.; Panov, V.B.; Ukhin, L.Yu.; Garnovskii, A.D.; Minkin, V.I.

1985-01-01

The reaction of N-alkyl-2,2'-dilithium diphenylamines with tellurium diiodide yields derivatives of a new heterocyclic system, phenotellurazine. 10-Alkyl-phenotellurazines readily form derivatives containing tetra- and tricoordinated tellurium, form complexes with metal salts and rhodium(I) carbonyl chloride and by bromination and nitration give 3,7-dibromo- or 3-nitro-, 3,7-dinitro, and 1,3,7,9-tetranitro derivatives

Enantioselective cyclizations and cyclization cascades of samarium ketyl radicals

Science.gov (United States)

Kern, Nicolas; Plesniak, Mateusz P.; McDouall, Joseph J. W.; Procter, David J.

2017-12-01

The rapid generation of molecular complexity from simple starting materials is a key challenge in synthesis. Enantioselective radical cyclization cascades have the potential to deliver complex, densely packed, polycyclic architectures, with control of three-dimensional shape, in one step. Unfortunately, carrying out reactions with radicals in an enantiocontrolled fashion remains challenging due to their high reactivity. This is particularly the case for reactions of radicals generated using the classical reagent, SmI2. Here, we demonstrate that enantioselective SmI2-mediated radical cyclizations and cascades that exploit a simple, recyclable chiral ligand can convert symmetrical ketoesters to complex carbocyclic products bearing multiple stereocentres with high enantio- and diastereocontrol. A computational study has been used to probe the origin of the enantioselectivity. Our studies suggest that many processes that rely on SmI2 can be rendered enantioselective by the design of suitable ligands.

Reacciones transfusionales mediadas inmunológicamente immunologically mediated transfusional reactions

Directory of Open Access Journals (Sweden)

Elkín Ferdinand Cardona Duque

2001-01-01

Full Text Available Son muchas las complicaciones potenciales de la terapia transfusional, pero la mayoría se presentan en pacientes que requieren múltiples transfusiones. Los riesgos asociados con la transfusión de una unidad sanguínea son realmente bajos pero deben considerarse contra los beneficios que se buscan al ordenarla. Las reacciones transfusionales se pueden clasificar como inmunológicas y no inmunológicas. Muchas de las primeras son causadas por estimulación de los anticuerpos por parte de los antígenos presentes en la transfusión de glóbulos rojos, leucocitos, plaquetas o proteínas del plasma. Esa isoinmunización puede llevar a una reacción futura cuando dichos antígenos sean transfundidos nuevamente al paciente. Entre las posibilidades se incluyen la hemólisis por incompatibilidad; las reacciones febriles o pulmonares causadas por antígenos en las plaquetas o los leucocitos; los fenómenos alérgicos o anafilácticos debidos a anticuerpos que reaccionan con antígenos solubles, generalmente del tipo de proteínas plasmáticas, y otras de menor importancia. The potential complications of blood transfusion therapy are multiple but most of them occur only in patients requiring repeated transfusions. Risks associated with transfusion of a single unit of blood are low; however, they must be weighted against the benefits at the time each transfusion is ordered. Transfusion reactions can be classified as either immunologic or non-immunologic. Many immune reactions are caused by stimulation of antibody production by foreign alloantigens present on transfused red cells, leukocytes, platelets, or plasma proteins. Such alloimmunization may lead to future immunologically mediated reactions when transfusions carrying these antigens are administered. These include hemolytic reactions caused by red blood cell incompatibility; febrile or pulmonary reactions caused by leukocytes and platelet antigens; allergic or anaphylactic reactions caused by

Bridge mediated two-electron transfer reactions: Analysis of stepwise and concerted pathways

International Nuclear Information System (INIS)

Petrov, E.G.; May, V.

2004-01-01

A theory of nonadiabatic donor (D)-acceptor (A) two-electron transfer (TET) mediated by a single regular bridge (B) is developed. The presence of different intermediate two-electron states connecting the reactant state D -- BA with the product state DBA -- results in complex multiexponential kinetics. The conditions are discussed at which a reduction to two-exponential as well as single-exponential kinetics becomes possible. For the latter case the rate K TET is calculated, which describes the bridge-mediated reaction as an effective two-electron D-A transfer. In the limit of small populations of the intermediate TET states D - B - A, DB -- A, D - BA - , and DB - A - , K TET is obtained as a sum of the rates K TET (step) and K TET (sup) . The first rate describes stepwise TET originated by transitions of a single electron. It starts at D -- BA and reaches DBA -- via the intermediate state D - BA - . These transitions cover contributions from sequential as well as superexchange reactions all including reduced bridge states. In contrast, a specific two-electron superexchange mechanism from D -- BA to DBA -- defines K TET (sup) . An analytic dependence of K TET (step) and K TET (sup) on the number of bridging units is presented and different regimes of D-A TET are studied

Protein tyrosine phosphatase 1B (PTP1B) is dispensable for IgE-mediated cutaneous reaction in vivo.

Science.gov (United States)

Yang, Ting; Xie, Zhongping; Li, Hua; Yue, Lei; Pang, Zheng; MacNeil, Adam J; Tremblay, Michel L; Tang, Jin-Tian; Lin, Tong-Jun

2016-01-01

Mast cells play a critical role in allergic reactions. The cross-linking of FcεRI-bound IgE with multivalent antigen initiates a cascade of signaling events leading to mast cell activation. It has been well-recognized that cross linking of FcεRI mediates tyrosine phosphorylation. However, the mechanism involved in tyrosine dephosphorylation in mast cells is less clear. Here we demonstrated that protein tyrosine phosphatase 1B (PTP1B)-deficient mast cells showed increased IgE-mediated phosphorylation of the signal transducer and activator of transcription 5 (STAT5) and enhanced production of CCL9 (MIP-1γ) and IL-6 in IgE-mediated mast cells activation in vitro. However, IgE-mediated calcium mobilization, β-hexaosaminidase release (degranulation), and phosphorylation of IκB and MAP kinases were not affected by PTP1B deficiency. Furthermore, PTP1B deficient mice showed normal IgE-dependent passive cutaneous anaphylaxis and late phase cutaneous reactions in vivo. Thus, PTP1B specifically regulates IgE-mediated STAT5 pathway, but is redundant in influencing mast cell function in vivo. Copyright © 2016 Elsevier Inc. All rights reserved.

Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

Energy Technology Data Exchange (ETDEWEB)

Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry

2004-09-15

One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

The dynamics of the laser-induced metal-semiconductor phase transition of samarium sulfide (SmS)

International Nuclear Information System (INIS)

Kaempfer, Tino

2009-01-01

The present thesis is dedicated to the experimental study of the metal-semiconductor phase transition of samarium sulfide (SmS): Temperature- and time-resolved experiments on the characterization of the phase transition of mixed-valence SmS samples (M-SmS) are presented. The measurement of the dynamics of the laser-induced phase transition pursues via time-resolved ultrashort-time microscopy and by X-ray diffraction with sub-picosecond time resolution. The electronic and structural processes, which follow an excitation of M-SmS with infrared femtosecond laser pulses, are physically interpreted on the base of the results obtained in this thesis and model imaginations. [de

The Influence of Receptor-Mediated Interactions on Reaction-Diffusion Mechanisms of Cellular Self-organisation

Czech Academy of Sciences Publication Activity Database

Klika, Václav; Baker, R. E.; Headon, D.; Gaffney, E. A.

2012-01-01

Roč. 74, č. 4 (2012), s. 935-957 ISSN 0092-8240 Institutional research plan: CEZ:AV0Z20760514 Keywords : reaction-diffusion * receptor-mediated patterning * turing models Subject RIV: BO - Biophysics Impact factor: 2.023, year: 2012 http://www.springerlink.com/content/9713544x6871w4n6/?MUD=MP

Samarium (III Selective Membrane Sensor Based on Tin (IV Boratophosphate

Directory of Open Access Journals (Sweden)

Ashok S. K. Kumar

2004-08-01

Full Text Available Abstract: A number of Sm (III selective membranes of varying compositions using tin (IV boratophosphate as electroactive material were prepared. Polyvinyl chloride, polystyrene and epoxy resin were used as binding materials. Membrane having composition of 40% exchanger and 60% epoxy resin exhibited best performance. This membrane worked well over a wide concentration range of 1x10-5M to 1x10-1 M of samarium ions with a Super-Nernstian slope of 40 mV/decade. It has a fast response time of less than 10 seconds and can be used for at least six months without any considerable divergence in potentials. The proposed sensor revealed good selectivities with respect to alkali, alkaline earth, some transition and rare earth metal ions and can be used in the pH range of 4.0-10.0. It was used as an indicator electrode in the potentiometric titration of Sm (III ions against EDTA. Effect of internal solution was studied and the electrode was successfully used in non-aqueous media, too.

A route to hydroxylfluorenes: TsOH-mediated condensation reactions of 1,3-diketones with propargylic alcohols

KAUST Repository

Yao, Liangfeng; Tan, Davin; Miao, Xiaohe; Huang, Kuo-Wei

2012-01-01

An efficient method of preparing hydroxylfluorenes by TsOH-mediated tandem alkylation/rearrangements of propargylic alcohols with 1,3-diketones is described. These reactions are accomplished in moderate to good yields under mild conditions to offer

Pathophysiology of neutrophil-mediated extracellular redox reactions.

Science.gov (United States)

Jaganjac, Morana; Cipak, Ana; Schaur, Rudolf Joerg; Zarkovic, Neven

2016-01-01

Neutrophil granulocyte leukocytes (neutrophils) play fundamental role in the innate immune response. In the presence of adequate stimuli, neutrophils release excessive amount of reactive oxygen species (ROS) that may induce cell and tissue injury. Oxidative burst of neutrophils acts as a double-edged sword. It may contribute to the pathology of atherosclerosis and brain injury but is also necessary in resolving infections. Moreover, neutrophil-derived ROS may also have both a tumor promoting and tumor suppressing role. ROS have a specific activities and diffusion distance, which is related to their short lifetime. Therefore, the manner in which ROS will act depends on the cells targeted and the intra- and extracellular levels of individual ROS, which can further cause production of reactive aldehydes like 4-hydroxynonenal (HNE) that act as a second messengers of ROS. In this review we discuss the influence of neutrophil mediated extracellular redox reactions in ischemia reperfusion injury, transplant rejection and chronic diseases (atherosclerosis, inflammatory bowel diseases and cancer). At the end a brief overview of cellular mechanisms to maintain ROS homeostasis is given.

Novel Chiral Bis-Phosphoramides as Organocatalysts for Tetrachlorosilane-Mediated Reactions

Directory of Open Access Journals (Sweden)

Sergio Rossi

2017-12-01

Full Text Available The formation of novel chiral bidentate phosphoroamides structures able to promote Lewis base-catalyzed Lewis acid-mediated reactions was investigated. Two different classes of phosphoroamides were synthetized: the first class presents a phthalic acid/primary diamine moiety, designed with the aim to perform a self-assembly recognition process through hydrogen bonds; the second one is characterized by the presence of two phosphoroamides as side arms connected to a central pyridine unit, able to chelate SiCl4 in a 2:1 adduct. These species were tested as organocatalysts in the stereoselective allylation of benzaldehyde and a few other aromatic aldehydes with allyl tributyltin in the presence of SiCl4 with good results. NMR studies confirm that only pyridine-based phosphoroamides effectively coordinate tetrachlorosilane and may lead to the generation of a self-assembled entity that would act as a promoter of the reaction. Although further work is necessary to clarify and confirm the formation of the hypothesized adduct, the study lays the foundation for the design and the synthesis of chiral supramolecular organocatalysts.

Determination of trace amounts of rare earth elements in samarium, terbium and disprosium oxides by graphite furnace atomic-absorption spectrometry

International Nuclear Information System (INIS)

Dantas, E.S.K.

1990-01-01

A graphite furnace atomic-absorption spectrometry method for the determination of neodymium, europium, terbium, dysprosium and yttrium at trace level in samarium oxide; of samarium, europium, dysprosium, holmium, erbium and yttrium in terbium oxide and of europium, terbium, holmium, erbium and yttrium in dysprosium oxide was established. The best pyrolysis and atomization temperatures were determined for each lanthanide considered. Calibration curves were obtained for the pure elements, for binary mixtures formed by the matrix and each of the lanthanides studied and, finally, for the complex mixtures constituted by the matrix and all the other lanthanide of the group under scrutiny. This study has been carried out to examine the interference of the presence of one lanthanide on the behaviour of the other, since a lack of linearity on the calibration curves has been observed in some cases. Detection and determination limits have been determined as well. The detection limits encountered were within the range 0.002 to 0.3% for different elements. The precision of the method expressed as the relative standard deviation was calculated for each element present in each of the matrices studied. The conclusion arrived at is that the method can be applied for determining the above mentioned lanthanides present in the matrices studied with purity up to 99.50%. (author)

Interest of uranium complexes for the mechanism study of the McMurry reaction; Interet des complexes de l`uranium pour l`etude du mecanisme de la reaction de McMurry

Energy Technology Data Exchange (ETDEWEB)

Maury, O

1997-07-04

The reducing coupling reactions of ketones in diols and olefins are generally carried out with titanium or samarium compounds. In this work uranium complexes have been used. They have allowed to study the chemical reaction mechanism. This thesis is divided into three parts: 1) the reduction mechanism of uranium tetrachloride by cyclic voltametry has been studied at first. It has been shown that this reduction is followed by a transfer reaction of chlorides between the reduced specie of the higher electronic density and UCl . 2) In the second part is described: the synthesis, the crystal structure, the reactivity of the chemical agents, the stereochemistry of diols and alkenes formation and the pinacolisation reaction catalysis. 3) In the last part, the limits of the McMurry reaction are given by the study of the aromatic ketones pinacolisation reaction by-products. The obtained results show that the complexes of the metals which present a high reducing and oxo-philic (Ti, Sm, U..) character react in a similar way with the carbonyl compounds. If the uranium compounds are less used than those of the titanium in the field of the organic synthesis applications, they are precious auxiliaries and excellent models for reactions mechanisms study and for the synthesis methods optimization. (O.M.). 284 refs.

Ultrasound-mediated drug delivery by gas bubbles generated from a chemical reaction.

Science.gov (United States)

Lee, Sungmun; Al-Kaabi, Leena; Mawart, Aurélie; Khandoker, Ahsan; Alsafar, Habiba; Jelinek, Herbert F; Khalaf, Kinda; Park, Ji-Ho; Kim, Yeu-Chun

2018-02-01

Highly echogenic and ultrasound-responsive microbubbles such as nitrogen and perfluorocarbons have been exploited as ultrasound-mediated drug carriers. Here, we propose an innovative method for drug delivery using microbubbles generated from a chemical reaction. In a novel drug delivery system, luminol encapsulated in folate-conjugated bovine serum albumin nanoparticles (Fol-BSAN) can generate nitrogen gas (N 2 ) by chemical reaction when it reacts with hydrogen peroxide (H 2 O 2 ), one of reactive oxygen species (ROS). ROS plays an important role in the initiation and progression of cancer and elevated ROS have been observed in cancer cells both in vitro and in vivo. High-intensity focussed ultrasound (HIFU) is used to burst the N 2 microbubbles, causing site-specific delivery of anticancer drugs such as methotrexate. In this research, the drug delivery system was optimised by using water-soluble luminol and Mobil Composition of Matter-41 (MCM-41), a mesoporous material, so that the delivery system was sensitive to micromolar concentrations of H 2 O 2 . HIFU increased the drug release from Fol-BSAN by 52.9 ± 2.9% in 10 minutes. The cytotoxicity of methotrexate was enhanced when methotrexate is delivered to MDA-MB-231, a metastatic human breast cancer cell line, using Fol-BSAN with HIFU. We anticipate numerous applications of chemically generated microbubbles for ultrasound-mediated drug delivery.

Interest of uranium complexes for the mechanism study of the McMurry reaction

International Nuclear Information System (INIS)

Maury, O.

1997-01-01

The reducing coupling reactions of ketones in diols and olefins are generally carried out with titanium or samarium compounds. In this work uranium complexes have been used. They have allowed to study the chemical reaction mechanism. This thesis is divided into three parts: 1) the reduction mechanism of uranium tetrachloride by cyclic voltametry has been studied at first. It has been shown that this reduction is followed by a transfer reaction of chlorides between the reduced specie of the higher electronic density and UCl . 2) In the second part is described: the synthesis, the crystal structure, the reactivity of the chemical agents, the stereochemistry of diols and alkenes formation and the pinacolisation reaction catalysis. 3) In the last part, the limits of the McMurry reaction are given by the study of the aromatic ketones pinacolisation reaction by-products. The obtained results show that the complexes of the metals which present a high reducing and oxo-philic (Ti, Sm, U..) character react in a similar way with the carbonyl compounds. If the uranium compounds are less used than those of the titanium in the field of the organic synthesis applications, they are precious auxiliaries and excellent models for reactions mechanisms study and for the synthesis methods optimization. (O.M.)

Fabrication of a PVC membrane samarium(III) sensor based on N,N Prime ,N Double-Prime -tris(4-pyridyl)trimesic amide as a selectophore

Energy Technology Data Exchange (ETDEWEB)

Zamani, Hassan Ali, E-mail: haszamani@yahoo.com [Department of Applied Chemistry, Mashhad Branch, Islamic Azad University, Mashhad (Iran, Islamic Republic of); Naghavi-Reyabbi, Fatemeh [Resident of General Surgery, Endoscopic and Minimaly Invasive Surgery Research Center, Ghaem Hospital, Faculty of Medicine, Mashhad University of Medical Sciences, Mashhad (Iran, Islamic Republic of); Faridbod, Farnoush [Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran (Iran, Islamic Republic of); Mohammadhosseini, Majid [Department of Chemistry, Faculty of Basic Sciences, Shahrood Branch, Islamic Azad University, Shahrood (Iran, Islamic Republic of); Ganjali, Mohammad Reza [Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran (Iran, Islamic Republic of); Tadjarodi, Azadeh; Rad, Maryam [Department of Chemistry, Iran University of Science and Technology, Tehran (Iran, Islamic Republic of)

2013-03-01

A new ion-selective electrode for Sm{sup 3+} ion is described based on the incorporation of N,N Prime ,N Double-Prime -tris(4-pyridyl)trimesic amide (TPTA) in a poly(vinylchloride) (PVC) matrix. The membrane sensor comprises nitrobenzene (NB) as a plasticizer, and oleic acid (OA) as an anionic additive. The sensor with the optimized composition shows a Nernstian potential response of 19.8 {+-} 0.5 mV decade{sup -1} over a wide concentration range of 1.0 Multiplication-Sign 10{sup -2} and 1 Multiplication-Sign 10{sup -6} mol L{sup -1}, with a lower detection limit of 4.7 Multiplication-Sign 10{sup -7} mol L{sup -1} and satisfactor applicable pH range of 3.6-9.2. Having a short response time of less than 10 s and a very good selectivity towards the Sm{sup 3+} over a wide variety of interfering cations (e.g. alkali, alkaline earth, transition and heavy metal ions) the sensor seemed to be a promising analytical tool for determination of the Sm{sup 3+}. Hence, it was used as an indicator electrode in the potentiometric titration of samarium ion with EDTA. It was also applied to the direct samarium recovery in binary mixtures. - Highlights: Black-Right-Pointing-Pointer A new Sm{sup 3+}-PVC membrane sensor is introduced for determination of Sm{sup 3+} ions in the solutions. Black-Right-Pointing-Pointer N,N Prime ,N Double-Prime -tris(4-pyridyl)trimesic amide was used as a suitable selectophore for samarium sensor. Black-Right-Pointing-Pointer Detection limit of the sensor is 4.7 Multiplication-Sign 10{sup -7} mol L{sup -1} with a short response time of less than 10 s.

Assault-related shame mediates the association between negative social reactions to disclosure of sexual assault and psychological distress.

Science.gov (United States)

DeCou, Christopher R; Cole, Trevor T; Lynch, Shannon M; Wong, Maria M; Matthews, Kathleen C

2017-03-01

Several studies have identified associations between social reactions to disclosure of sexual assault and psychological distress; however, no studies have evaluated shame as a mediator of this association. This study evaluated assault-related shame as a mediator of the associations between negative social reactions to disclosure of sexual assault and symptoms of posttraumatic stress disorder (PTSD), depression, and global distress and hypothesized that there would be an indirect effect of social reactions to disclosure upon symptoms of psychopathology via assault-related shame. Participants were 207 female psychology undergraduates who reported past history of completed or attempted sexual assault and had disclosed the assault to at least 1 other person. Participants completed self-report measures of social reactions to sexual assault disclosure, assault-related shame, and symptoms of psychopathology. Participants reported significant histories of attempted or completed sexual assault and indicated clinically significant symptoms of depression and subthreshold symptoms of PTSD and global distress, on average. Evaluation of structural models confirmed the hypothesized indirect effect of negative social reactions to sexual assault disclosure upon symptoms of PTSD (z = 5.85, p distress (z = 4.82, p disclosure among survivors of attempted or completed sexual assault. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Food allergens inducing a lymphocyte-mediated immunological reaction in canine atopic-like dermatitis.

Science.gov (United States)

Suto, Akemi; Suto, Yukinori; Onohara, Nozomi; Tomizawa, Yu; Yamamoto-Sugawara, Yukiko; Okayama, Taro; Masuda, Kenichi

2015-02-01

Canine atopic-like dermatitis (ALD) is suspected to be associated with food allergies, particularly those mediated by lymphocytes. In this study, 54 cases were included as ALD dogs, based on the negative IgE test results. In the dogs, the percentage of activated cells in helper-T lymphocytes was measured by flow cytometry using cultured peripheral lymphocytes under food allergen stimulation. We observed that 49 of the 54 ALD dogs (90.7%) had positive lymphocyte reactions against one or more food allergens. The most common food allergen was soybean, showing positive results in 21 dogs (42.9%), while the allergen to cause the lowest number of reactions was catfish (only 5 dogs, 10.2%). These results may be useful in considering elimination diets for ALD dogs.

Fluorometric determination of samarium and europium in rare earth minerals with. beta. -diketoneternary complex

Energy Technology Data Exchange (ETDEWEB)

Huang, H; Hiraki, K; Nishikawa, Y [Kinki Univ., Higashi-Osaka, Osaka (Japan). Faculty of Science and Technology

1981-07-01

This communication reported the optimum conditions for the fluorometric determination of these ions, and the method was adopted in the simultaneous determination of samarium and europium in xenotime and monazite minerals. From the experimental results on the effect of diverse ions and the extraction pH of the aqueous phase, it became clear that TTA-TOPO hexane method was the best system for the determination of samarium and europium because of the highest fluorescence sensitivity of the ternary complex, and also because the lower extraction pH eliminated the effect of diverse ions. Moreover, the very high detection limit (2 ppb) of Sm was achieved by the use of a red sensitive photomultiplier. Which was used at 644 nm, and that of Eu (0.02 ppb) at 614 nm. The procedure was established as follows: The rare earth minerals (xenotime, monazite) sample was treated with hot conc. H/sub 2/SO/sub 4/ and twice precipitated with 0.5 mol dm/sup -3/ oxalic acid (pH was adjusted to 2.0 -- 2.2). Then the precipitate was filtered and ignited to give the rare earth oxide. Fifty milligrams of the oxide was dissolved in HCl and diluted with water in order to obtain the solution containing 5 ..mu..g cm/sup -3/ rare earth oxide. An aliquot of the solution ((1.0 -- 3.0) cm/sup 3/) was adjusted to pH 5.5 with sodium acetate and shaken with 1 x 10/sup -4/ mol dm/sup -3/ TTA- 2 x 10/sup -2/ mol dm/sup -3/ TOPO hexane solution. Then the fluorescence intensity of the organic layer was measured at 644 nm for Sm and 614 nm for Eu. In this procedure, the recovery of Sm and Eu was found to be about 96%. Xenotime contained 0.70% of Sm and 0.004% of Eu, and monazite contained 1.84% of Sm and 0.003% of Eu.

Biochemical identification of residues that discriminate between 3,4-dihydroxyphenylalanine decarboxylase and 3,4-dihydroxyphenylacetaldehyde synthase-mediated reactions.

Science.gov (United States)

Liang, Jing; Han, Qian; Ding, Haizhen; Li, Jianyong

2017-12-01

In available insect genomes, there are several L-3,4-dihydroxyphenylalanine (L-dopa) decarboxylase (DDC)-like or aromatic amino acid decarboxylase (AAAD) sequences. This contrasts to those of mammals whose genomes contain only one DDC. Our previous experiments established that two DDC-like proteins from Drosophila actually mediate a complicated decarboxylation-oxidative deamination process of dopa in the presence of oxygen, leading to the formation of 3,4-dihydroxyphenylacetaldehyde (DHPA), CO 2 , NH 3, and H 2 O 2 . This contrasts to the typical DDC-catalyzed reaction, which produces CO 2 and dopamine. These DDC-like proteins were arbitrarily named DHPA synthases based on their critical role in insect soft cuticle formation. Establishment of reactions catalyzed by these AAAD-like proteins solved a puzzle that perplexed researchers for years, but to tell a true DHPA synthase from a DDC in the insect AAAD family remains problematic due to high sequence similarity. In this study, we performed extensive structural and biochemical comparisons between DHPA synthase and DDC. These comparisons identified several target residues potentially dictating DDC-catalyzed and DHPA synthase-catalyzed reactions, respectively. Comparison of DHPA synthase homology models with crystal structures of typical DDC proteins, particularly residues in the active sites, provided further insights for the roles these identified target residues play. Subsequent site-directed mutagenesis of the tentative target residues and activity evaluations of their corresponding mutants determined that active site His192 and Asn192 are essential signature residues for DDC- and DHPA synthase-catalyzed reactions, respectively. Oxygen is required in DHPA synthase-mediated process and this oxidizing agent is reduced to H 2 O 2 in the process. Biochemical assessment established that H 2 O 2 , formed in DHPA synthase-mediated process, can be reused as oxidizing agent and this active oxygen species is reduced to H 2

Assessing the reaction conditions to mediate the milkfat-soybean oil enzymatic interesterification

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Ariela Veloso de Paula

Full Text Available Summary A food grade lipase from Rhizopus oryzae immobilized on a hybrid polysiloxane-polyvinyl alcohol matrix (SiO2-PVA was used as the biocatalyst to mediate the interesterification reactions of a blend containing 65% milkfat and 35% soybean oil. All the reactions occurred in an inert nitrogen atmosphere in cylindrical glass reactors (80 mL with 40 g of the milkfat-soybean oil blend. The influence of the following variables was evaluated: biocatalyst loading (250-1500 activity units per gram of blend, biocatalyst moisture content (5-20%, temperature (45-60 °C and incubation time (2-48 h. The reactions were monitored by determining the free fatty acid content, triacylglycerol (TAGs composition in carbon species, and the consistency of the interesterified (IE products. The reaction conditions were set based on the parameters that provided a high interesterification yield and good consistency of the final product within the ideal range (200 to 800 gf cm-2. Hence the best results were obtained using a biocatalyst loading of 500 U g-1 of blend with 10% moisture content at 45 °C for 4 h. Under these conditions the consistency of the interesterified product was 539.7 ± 38 gf cm-2. The results demonstrated the potential of the immobilized lipase to alter the TAGs profile of the milkfat-soybean oil blend, allowing for the production of structured lipids.

A catalyst-free addition reaction of zinc amide enolates to N-sulfonyle imines

Energy Technology Data Exchange (ETDEWEB)

Joo, Seong Ryu; Im, Pyeong Won; Kim, Jong Sung; Kim, Seung Hoi [Dept. of Chemistry, Dankook University, Cheonan (Korea, Republic of); Park Soo Youl [Interface Chemistry and Engineering Research Team, Korea Research Institute of Chemical Technology, Daejon (Korea, Republic of)

2016-12-15

Despite the remarkable expansion of the imino-Reformatsky reaction, one interesting aspect is that, to the best of our knowledge, zinc enolates derived solely from α-halo esters have been mainly used in the recent progress. In contrast, a few limited examples have been reported concerning the application of zinc enolates derived from α-halo amide to the imino-Reformatsky reaction. In recent years, Rodriguez-Solla and co-workers reported the addition reaction of samarium enolates derived from both α-halo esters and amides to imines, resulting in the synthe- sis of β-amino esters or amides. In conclusion, we established a potential synthetic proto- col for the preparation of β-amino amides. This work was accomplished by the direct addition of zinc amide enolates to N-sulfonyl imines in the absence of any metal-catalyst under mild conditions. Due to the operational simplicity of the proposed method, it can be further utilized in synthetic organic chemistry. Further studies to elucidate the scope of this approach are currently underway in our laboratory.

A catalyst-free addition reaction of zinc amide enolates to N-sulfonyle imines

International Nuclear Information System (INIS)

Joo, Seong Ryu; Im, Pyeong Won; Kim, Jong Sung; Kim, Seung Hoi; Park Soo Youl

2016-01-01

Despite the remarkable expansion of the imino-Reformatsky reaction, one interesting aspect is that, to the best of our knowledge, zinc enolates derived solely from α-halo esters have been mainly used in the recent progress. In contrast, a few limited examples have been reported concerning the application of zinc enolates derived from α-halo amide to the imino-Reformatsky reaction. In recent years, Rodriguez-Solla and co-workers reported the addition reaction of samarium enolates derived from both α-halo esters and amides to imines, resulting in the synthe- sis of β-amino esters or amides. In conclusion, we established a potential synthetic proto- col for the preparation of β-amino amides. This work was accomplished by the direct addition of zinc amide enolates to N-sulfonyl imines in the absence of any metal-catalyst under mild conditions. Due to the operational simplicity of the proposed method, it can be further utilized in synthetic organic chemistry. Further studies to elucidate the scope of this approach are currently underway in our laboratory

RhoA/ROCK Signaling Pathway Mediates Shuanghuanglian Injection-Induced Pseudo-allergic Reactions.

Science.gov (United States)

Han, Jiayin; Zhao, Yong; Zhang, Yushi; Li, Chunying; Yi, Yan; Pan, Chen; Tian, Jingzhuo; Yang, Yifei; Cui, Hongyu; Wang, Lianmei; Liu, Suyan; Liu, Jing; Deng, Nuo; Liang, Aihua

2018-01-01

SHLI-induced hypersensitivity reactions in both endothelial cells and mice indicating its protective effect. SHLI-induced pseudo-allergic reactions were mediated by the activation of the RhoA/ROCK signaling pathway. Conclusion : This study presents a novel mechanism of SHLI-induced immediate hypersensitivity reactions and suggests a potential therapeutic strategy to prevent the associated adverse reactions.

Mediating and Moderating Effects in Ageism and Depression among the Korean Elderly: The Roles of Emotional Reactions and Coping Reponses

Science.gov (United States)

Kim, Il-Ho; Noh, Samuel; Chun, Heeran

2015-01-01

Objectives This study evaluated the relationship between ageism and depression, exploring the stress-mediating and stress-moderating roles of emotional reactions and coping behaviors. Methods Data were from the 2013 Ageism and Health Study (n = 816), a cross-sectional survey of urban and rural community-dwelling seniors aged 60–89 years in South Korea. Participants with at least one experience of ageism reported on their emotional reactions and coping responses. The measure yielded two types of coping: problem-focused (taking formal action, confrontation, seeking social support) and emotion-focused (passive acceptance, emotional discharge). Results Although ageism was significantly associated with depressive symptoms (B = 0.27, p < 0.0001), the association was entirely mediated by emotional reactions such as anger, sadness, and powerlessness. Problem-focused coping, especially confrontation and social support, seemingly reduced the impact of emotional reactions on depression, whereas emotion-focused coping exacerbated the adverse effects. Conclusion These findings support the cultural characterization explanation of ageism and related coping processes among Korean elderly and suggest that regulating emotional reactions may determine the efficacy of coping with ageism. PMID:26981336

Food allergens inducing a lymphocyte-mediated immunological reaction in canine atopic-like dermatitis

OpenAIRE

SUTO, Akemi; SUTO, Yukinori; ONOHARA, Nozomi; TOMIZAWA, Yu; YAMAMOTO-SUGAWARA, Yukiko; OKAYAMA, Taro; MASUDA, Kenichi

2014-01-01

Canine atopic-like dermatitis (ALD) is suspected to be associated with food allergies, particularly those mediated by lymphocytes. In this study, 54 cases were included as ALD dogs, based on the negative IgE test results. In the dogs, the percentage of activated cells in helper-T lymphocytes was measured by flow cytometry using cultured peripheral lymphocytes under food allergen stimulation. We observed that 49 of the 54 ALD dogs (90.7%) had positive lymphocyte reactions against one or more f...

Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

International Nuclear Information System (INIS)

Li, Jianhua; Peng, Jianbiao; Zhang, Ya; Ji, Yuefei; Shi, Huanhuan; Mao, Liang; Gao, Shixiang

2016-01-01

Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H_2O_2 concentration and enzyme dosage affected the removal efficiency of TCS. • The removal of TCS by SBP was more efficient than that of HRP. • K_C_A_T and K_C_A_T/K_M values for SBP toward TCS were much higher than those for HRP. • Polymers formed via radical coupling mechanism were nontoxic to the growth of alga. - Abstract: This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H_2O_2 concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H_2O_2 concentration, while the optimal pH and H_2O_2 concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL"−"1 SBP in 30 min reaction time, while an HRP dose of 0.3 U mL"−"1 was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (K_C_A_T) and catalytic efficiency (K_C_A_T/K_M) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via C−C and C−O coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water/wastewater treatment.

Enhanced bimolecular exchange reaction through programmed coordination of a five-coordinate oxovanadium complex for efficient redox mediation in dye-sensitized solar cells.

Science.gov (United States)

Oyaizu, Kenichi; Hayo, Noriko; Sasada, Yoshito; Kato, Fumiaki; Nishide, Hiroyuki

2013-12-07

Electrochemical reversibility and fast bimolecular exchange reaction found for VO(salen) gave rise to a highly efficient redox mediation to enhance the photocurrent of a dye-sensitized solar cell, leading to an excellent photovoltaic performance with a conversion efficiency of 5.4%. A heterogeneous electron-transfer rate constant at an electrode (k0) and a second-order rate constant for an electron self-exchange reaction (k(ex)) were proposed as key parameters that dominate the charge transport property, which afforded a novel design concept for the mediators based on their kinetic aspects.

Work-Family Conflict and Work-Related Attitude: The Mediating Effects of Stress Reactions

Directory of Open Access Journals (Sweden)

Siti Aisyah Binti Panatik

2012-01-01

Full Text Available This study aims to investigate the relationship between work-family conflict (i.e.work-to-family and family-to-work and work-related attitudes (i.e. job satisfaction,affective commitment and turnover intentions among academician in Malaysia.Mediationeffects of stress reactionswhich arebehavioral stress, somatic stress andcognitive stresswere also tested. A survey method using questionnaire was utilizedto obtain the data. A total of 267 respondents were participated, giving the return rateof 20% from the entire ofpopulation. Research data were analyzed using PASW18and AMOS SPSS18.Result indicated that onlywork-to-family conflict wassignificantly related to stress reactions.While, behavioral stress mediates the effectsof work-to-family conflict on job satisfaction, affective commitment and turnoverintentions. Cognitive stress only mediates the effects of work-to-family conflict onaffective commitment. This paper also discusses the implication of this study to theorganization and future research.

The properties of samarium-doped zinc oxide/phthalocyanine structure for optoelectronics prepared by pulsed laser deposition and organic molecular evaporation

Czech Academy of Sciences Publication Activity Database

Novotný, Michal; Marešová, Eva; Fitl, Přemysl; Vlček, Jan; Bergmann, M.; Vondráček, Martin; Yatskiv, Roman; Bulíř, Jiří; Hubík, Pavel; Hruška, Petr; Drahokoupil, Jan; Abdellaoui, N.; Vrňata, M.; Lančok, Ján

2016-01-01

Roč. 122, č. 3 (2016), 1-8, č. článku 225. ISSN 0947-8396 R&D Projects: GA MŠk(CZ) LG15050; GA ČR(CZ) GAP108/11/0958; GA MŠk(CZ) LM2011029; GA ČR(CZ) GA14-10279S; GA MŠk(CZ) 7AMB14FR010 Institutional support: RVO:68378271 ; RVO:67985882 Keywords : samarium-doped zinc oxide zinc/phthalocyanine deposition * evaporation * pulsed laser deposition * thin films Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.455, year: 2016

Charge and transition densities of samarium isotopes in the interacting Boson model

International Nuclear Information System (INIS)

Moinester, M.A.; Alster, J.; Dieperink, A.E.L.

1982-01-01

The interacting boson approximation (IBA) model has been used to interpret the ground-state charge distributions and lowest 2 + transition charge densities of the even samarium isotopes for A = 144-154. Phenomenological boson transition densities associated with the nucleons comprising the s-and d-bosons of the IBA were determined via a least squares fit analysis of charge and transition densities in the Sm isotopes. The application of these boson trasition densities to higher excited 0 + and 2 + states of Sm, and to 0 + and 2 + transitions in neighboring nuclei, such as Nd and Gd, is described. IBA predictions for the transition densities of the three lowest 2 + levels of 154 Gd are given and compared to theoretical transition densities based on Hartree-Fock calculations. The deduced quadrupole boson transition densities are in fair agreement with densities derived previously from 150 Nd data. It is also shown how certain moments of the best fit boson transition densities can simply and sucessfully describe rms radii, isomer shifts, B(E2) strengths, and transition radii for the Sm isotopes. (orig.)

Pyrovanadolysis: a Pyrophosphorolysis-like Reaction Mediated by Pyrovanadate MN2plus and DNA Polymerase of Bacteriophage T7

Energy Technology Data Exchange (ETDEWEB)

B Akabayov; A Kulczyk; S Akabayov; C Thiele; L McLaughlin; B Beauchamp; C Richardson

2011-12-31

DNA polymerases catalyze the 3'-5'-pyrophosphorolysis of a DNA primer annealed to a DNA template in the presence of pyrophosphate (PP{sub i}). In this reversal of the polymerization reaction, deoxynucleotides in DNA are converted to deoxynucleoside 5'-triphosphates. Based on the charge, size, and geometry of the oxygen connecting the two phosphorus atoms of PP{sub i}, a variety of compounds was examined for their ability to carry out a reaction similar to pyrophosphorolysis. We describe a manganese-mediated pyrophosphorolysis-like activity using pyrovanadate (VV) catalyzed by the DNA polymerase of bacteriophage T7. We designate this reaction pyrovanadolysis. X-ray absorption spectroscopy reveals a shorter Mn-V distance of the polymerase-VV complex than the Mn-P distance of the polymerase-PP{sub i} complex. This structural arrangement at the active site accounts for the enzymatic activation by Mn-VV. We propose that the Mn{sup 2+}, larger than Mg{sup 2+}, fits the polymerase active site to mediate binding of VV into the active site of the polymerase. Our results may be the first documentation that vanadium can substitute for phosphorus in biological processes.

IgE- and IgG mediated severe anaphylactic platelet transfusion reaction in a known case of cerebral malaria

Directory of Open Access Journals (Sweden)

B Shanthi

2013-01-01

Full Text Available Background: Allergic reactions occur commonly in transfusion practice. However, severe anaphylactic reactions are rare; anti-IgA (IgA: Immunoglobulin A in IgA-deficient patients is one of the well-illustrated and reported causes for such reactions. However, IgE-mediated hypersensitivity reaction through blood component transfusion may be caused in parasitic hyperimmunization for IgG and IgE antibodies. Case Report: We have evaluated here a severe anaphylactic transfusion reaction retrospectively in an 18year-old male, a known case of cerebral malaria, developed after platelet transfusions. The examination and investigations revealed classical signs and symptoms of anaphylaxis along with a significant rise in the serum IgE antibody level and IgG by hemagglutination method. Initial mild allergic reaction was followed by severe anaphylactic reaction after the second transfusion of platelets. Conclusion: Based on these results, screening of patients and donors with mild allergic reactions to IgE antibodies may help in understanding the pathogenesis as well as in planning for preventive desensitization and measures for safe transfusion.

Talking about suicide may not be enough: family reaction as a mediator between disclosure and interpersonal needs.

Science.gov (United States)

Frey, Laura M; Fulginiti, Anthony

2017-08-01

Although most people who make an attempt do not die, attempt survivors remain at particularly elevated risk for suicide in the short- and long-term. Moreover, the research on suicide-related disclosure and subsequent family reactions on risk factors for the development of suicidal desire is limited. This study examined the relationships between disclosure, family reaction and two interpersonal needs connected to the development of suicidal desire. Data from 74 attempt survivors who participated in a larger study were analyzed to assess the relationships between degree of suicide-related disclosure, quality of family reaction and thwarted belongingness and perceived burdensomeness. Results indicated that higher rates of disclosure predicted more positive family reactions, which in turn predicted lower levels of thwarted belongingness and perceived burdensomeness. Although there was no direct relationship between disclosure and the outcome variables, bootstrapping analyses indicated that family reaction mediated the relationship between disclosure and both belongingness and burdensomeness. These findings suggest the need for more family interventions that promote healthy reactions following suicide-related disclosure in order to facilitate the recovery and treatment process.

tri-n-butyltin hydride-mediated radical reaction of a 2-iodobenzamide: formation of an unexpected carbon-tin bond

International Nuclear Information System (INIS)

Oliveira, Marcelo T.; Alves, Rosemeire B.; Cesar, Amary; Prado, Maria Auxiliadora F.; Alves, Ricardo J.; Queiroga, Carla G.; Santos, Leonardo S.; Eberlin, Marcos N.

2007-01-01

The tri-n-butyltin hydride-mediated reaction of methyl 2,3-di-O-benzyl-4-O-trans-cinnamyl- 6-deoxy-6-(2-iodobenzoylamino)-α-D-galactopyranoside afforded an unexpected aryltributyltin compound. The structure of this new tetraorganotin(IV) product has been elucidated by 1 H, 13 C NMR spectroscopy, COSY and HMQC experiments and electrospray ionization mass spectrometry (ESI-MS). The formation of this new compound via a radical coupling reaction and a radical addition-elimination process is discussed. (author)

Universal, colorimetric microRNA detection strategy based on target-catalyzed toehold-mediated strand displacement reaction

Science.gov (United States)

Park, Yeonkyung; Lee, Chang Yeol; Kang, Shinyoung; Kim, Hansol; Park, Ki Soo; Park, Hyun Gyu

2018-02-01

In this work, we developed a novel, label-free, and enzyme-free strategy for the colorimetric detection of microRNA (miRNA), which relies on a target-catalyzed toehold-mediated strand displacement (TMSD) reaction. The system employs a detection probe that specifically binds to the target miRNA and sequentially releases a catalyst strand (CS) intended to trigger the subsequent TMSD reaction. Thus, the presence of target miRNA releases the CS that mediates the formation of an active G-quadruplex DNAzyme which is initially caged and inactivated by a blocker strand. In addition, a fuel strand that is supplemented for the recycling of the CS promotes another TMSD reaction, consequently generating a large number of active G-quadruplex DNAzymes. As a result, a distinct colorimetric signal is produced by the ABTS oxidation promoted by the peroxidase mimicking activity of the released G-quadruplex DNAzymes. Based on this novel strategy, we successfully detected miR-141, a promising biomarker for human prostate cancer, with high selectivity. The diagnostic capability of this system was also demonstrated by reliably determining target miR-141 in human serum, showing its great potential towards real clinical applications. Importantly, the proposed approach is composed of separate target recognition and signal transduction modules. Thus, it could be extended to analyze different target miRNAs by simply redesigning the detection probe while keeping the same signal transduction module as a universal signal amplification unit, which was successfully demonstrated by analyzing another target miRNA, let-7d.

Stratum corneum profiles of inflammatory mediators in patch test reactions to common contact allergens and sodium lauryl sulfate.

Science.gov (United States)

Koppes, S A; Ljubojevic Hadzavdic, S; Jakasa, I; Franceschi, N; Jurakić Tončić, R; Marinović, B; Brans, R; Gibbs, S; Frings-Dresen, M H W; Rustemeyer, T; Kezic, S

2017-06-01

Recent studies have demonstrated allergen-specific differences in the gene expression of inflammatory mediators in patch tested skin. To determine levels of various inflammatory mediators in the stratum corneum (SC) after patch testing with common contact allergens and the skin irritant sodium lauryl sulfate (SLS). In total, 27 individuals who had previously patch tested positive to nickel, chromium, methylchloroisothiazolinone/methylisothiazolinone (MCI/MI) or para-phenylenediamine were retested and then patch tested with SLS and petrolatum, with petrolatum serving as the patch test control. At 72 h, the test sites were clinically graded and the SC samples collected on adhesive tape. The levels of 18 of the 32 quantified mediators differed significantly from that of the control patches for at least one of the tested substances. SLS and MCI/MI induced the largest number of immunomediators. Interleukin (IL)-16 levels were significantly higher in patch test reactions in all allergens than they were in the controls, while no significant difference was detected for SLS. Furthermore, a strong negative correlation was found between strength of patch test reaction and IL-1α levels. Cytokine profiles in the SC of patch tested skin did not show a distinct allergen-specific pattern. However, MCI/MI induced a larger and wider immune response than the other allergens, perhaps due to its potency as an irritant. The levels of IL-16 were significantly increased in patch test reactions to allergens but not to SLS; thus, they may help clinicians to differentiate between allergic contact dermatitis and irritant contact dermatitis. © 2016 British Association of Dermatologists.

Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

Energy Technology Data Exchange (ETDEWEB)

Li, Jianhua; Peng, Jianbiao [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Zhang, Ya [Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection of the People’s Republic of China, Nanjing 210042 (China); Ji, Yuefei [College of Resources and Environmental Science, Nanjing Agricultural University, Nanjing 210095 (China); Shi, Huanhuan; Mao, Liang [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Gao, Shixiang, E-mail: ecsxg@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China)

2016-06-05

Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H{sub 2}O{sub 2} concentration and enzyme dosage affected the removal efficiency of TCS. • The removal of TCS by SBP was more efficient than that of HRP. • K{sub CAT} and K{sub CAT}/K{sub M} values for SBP toward TCS were much higher than those for HRP. • Polymers formed via radical coupling mechanism were nontoxic to the growth of alga. - Abstract: This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H{sub 2}O{sub 2} concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H{sub 2}O{sub 2} concentration, while the optimal pH and H{sub 2}O{sub 2} concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL{sup −1} SBP in 30 min reaction time, while an HRP dose of 0.3 U mL{sup −1} was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (K{sub CAT}) and catalytic efficiency (K{sub CAT}/K{sub M}) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via C−C and C−O coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water

Catalytic conversion reactions mediated by single-file diffusion in linear nanopores: hydrodynamic versus stochastic behavior.

Science.gov (United States)

Ackerman, David M; Wang, Jing; Wendel, Joseph H; Liu, Da-Jiang; Pruski, Marek; Evans, James W

2011-03-21

We analyze the spatiotemporal behavior of species concentrations in a diffusion-mediated conversion reaction which occurs at catalytic sites within linear pores of nanometer diameter. Diffusion within the pores is subject to a strict single-file (no passing) constraint. Both transient and steady-state behavior is precisely characterized by kinetic Monte Carlo simulations of a spatially discrete lattice-gas model for this reaction-diffusion process considering various distributions of catalytic sites. Exact hierarchical master equations can also be developed for this model. Their analysis, after application of mean-field type truncation approximations, produces discrete reaction-diffusion type equations (mf-RDE). For slowly varying concentrations, we further develop coarse-grained continuum hydrodynamic reaction-diffusion equations (h-RDE) incorporating a precise treatment of single-file diffusion in this multispecies system. The h-RDE successfully describe nontrivial aspects of transient behavior, in contrast to the mf-RDE, and also correctly capture unreactive steady-state behavior in the pore interior. However, steady-state reactivity, which is localized near the pore ends when those regions are catalytic, is controlled by fluctuations not incorporated into the hydrodynamic treatment. The mf-RDE partly capture these fluctuation effects, but cannot describe scaling behavior of the reactivity.

Efficacy and toxicity of Samarium-153-EDTMP locally produced in the treatment of painful skeletal metastases

International Nuclear Information System (INIS)

Olea, E.; Quintana, J.C.; Nagel, J.; Arenas, L.; Tomicic, M.; Gil, M.C.; Araya, G.

2001-01-01

Samarium-153 emits medium-energy beta particles an a gamma photon with a physical half-life of 46,3 hours. When chelated to ethylenediaminetetramethylenephosphonic acid (EDTMP), it is remarkably stable in vitro and in vivo. In this study we administered randomly 0,5 and 1,0 mCi/Kg body weight (two groups), to 30 patients with painful metastatic bone cancer. Slight and spontaneously reversible myelotoxicity was observed. A bigger leukocyte and platelet suppression was obtained with 1,0 mCi/kg than 0,5 mCi/Kg dose. Pain palliation was obtained in 66% of the treated patients. Our preliminary results indicate that 153 Sm-EDTMP is a promising radiotherapeutic agent for palliative treatment of metastatic bone cancer pain where a reactor is available and at a very affordable cost. (author)

Determination of the nuclear electric charge distribution of samarium isotopes 144, 148, 150, 152, 154 by the muonic atom method

International Nuclear Information System (INIS)

Barreau, Pierre.

1977-01-01

The theory of the nucleus-negative muon system in the case of electrical interactions is discussed. The interactions of muons with the samarium isotopes 152, 154, 144, 148, 150 are investigated. After a description of the experimental device, from muon beam production to data acquisition (detection of the gamma spectra), the results are analyzed and the nuclear charge distribution parameters determined: for each isotope the absolute value of c (half-density radius) and t (skin thickness); for 152 Sm and 154 Sm the parameter β 2 (quadrupolar defomation). Nuclear polarization was accounted for throughout the analysis [fr

Pharmacokinetics of labelled compounds with technetium-99m and samarium-153

International Nuclear Information System (INIS)

Borda O, L.B.; Torres L, M.N.

1997-01-01

The purpose of this investigation was to establish the different pharmacokinetics parameters of the main radiopharmaceuticals labeled with technetium-99m and samarium-153. These parameters could be subsequently used as reference to compare other products with the same use. Mathematical models and a computerized pharmacokinetic program were used to this purpose. A biodistribution study in quadruplicate and/or quintuplicate was conducted for each radiopharmaceutical, data was was obtained in injection dose percentages. The biodistribution study involved the injection of a predetermined dose of the radiopharmaceutical into animals (rats or mice), which were subsequently put away at different time intervals, removing the relevant organs. Activity in each organ was read by means of a well-type NaI scintillation counter, data obtained in activity counts was transformed into injection dose percentages. Based on these percentages, the mathematical model was constructed and the pharmacokinetic parameters were obtained using the computerized program Expo 2 v. 1, which is written in C language and works in windows. Analyzing the results obtained, we can conclude that the use of the Expo 2 v. 1 program for a bi compartmental analysis allowed us to obtain reliable pharmacokinetic parameters which describe what happens in the organism when the radiopharmaceutical passes from the central compartment to the peripheral one and vice versa

A route to hydroxylfluorenes: TsOH-mediated condensation reactions of 1,3-diketones with propargylic alcohols

KAUST Repository

Yao, Liangfeng

2012-01-01

An efficient method of preparing hydroxylfluorenes by TsOH-mediated tandem alkylation/rearrangements of propargylic alcohols with 1,3-diketones is described. These reactions are accomplished in moderate to good yields under mild conditions to offer a straightforward and convenient one step synthetic route to hydroxylfluorene derivatives through a plausible mechanism involving a sequence of dehydration, addition, rearrangement and aromatization. This journal is © The Royal Society of Chemistry 2012.

Radical-Mediated Enzymatic Polymerizations

Science.gov (United States)

Zavada, Scott R.; Battsengel, Tsatsral; Scott, Timothy F.

2016-01-01

Polymerization reactions are commonly effected by exposing monomer formulations to some initiation stimulus such as elevated temperature, light, or a chemical reactant. Increasingly, these polymerization reactions are mediated by enzymes―catalytic proteins―owing to their reaction efficiency under mild conditions as well as their environmental friendliness. The utilization of enzymes, particularly oxidases and peroxidases, for generating radicals via reduction-oxidation mechanisms is especially common for initiating radical-mediated polymerization reactions, including vinyl chain-growth polymerization, atom transfer radical polymerization, thiol–ene step-growth polymerization, and polymerization via oxidative coupling. While enzyme-mediated polymerization is useful for the production of materials intended for subsequent use, it is especially well-suited for in situ polymerizations, where the polymer is formed in the place where it will be utilized. Such polymerizations are especially useful for biomedical adhesives and for sensing applications. PMID:26848652

Studies on the structural, optical and dielectric properties of samarium coordinated with salicylic acid single crystal

Science.gov (United States)

Singh, Harjinder; Slathia, Goldy; Gupta, Rashmi; Bamzai, K. K.

2018-04-01

Samarium coordinated with salicylic acid was successfully grown as a single crystal by low temperature solution technique using mixed solvent of methanol and water in equal ratio. Structural characterization was carried out by single crystal X-ray diffraction analysis and it crystallizes in centrosymmetric space group P121/c1. FTIR and UV-Vis-NIR spectroscopy confirmed the compound formation and help to determine the mode of binding of the ligand to the rare earth-metal ion. Dielectric constant and dielectric loss have been measured over the frequency range 100 Hz - 30MHz. The decrease in dielectric constant with increases in frequency is due to the transition from interfacial polarization to dipolar polarization. The small value of dielectric constant at higher frequency ensures that the crystal is good candidate for NLO devices. Dielectric loss represents the resistive nature of the material.

Hapten-Induced Contact Hypersensitivity, Autoimmune Reactions, and Tumor Regression: Plausibility of Mediating Antitumor Immunity

Directory of Open Access Journals (Sweden)

Dan A. Erkes

2014-01-01

Full Text Available Haptens are small molecule irritants that bind to proteins and elicit an immune response. Haptens have been commonly used to study allergic contact dermatitis (ACD using animal contact hypersensitivity (CHS models. However, extensive research into contact hypersensitivity has offered a confusing and intriguing mechanism of allergic reactions occurring in the skin. The abilities of haptens to induce such reactions have been frequently utilized to study the mechanisms of inflammatory bowel disease (IBD to induce autoimmune-like responses such as autoimmune hemolytic anemia and to elicit viral wart and tumor regression. Hapten-induced tumor regression has been studied since the mid-1900s and relies on four major concepts: (1 ex vivo haptenation, (2 in situ haptenation, (3 epifocal hapten application, and (4 antigen-hapten conjugate injection. Each of these approaches elicits unique responses in mice and humans. The present review attempts to provide a critical appraisal of the hapten-mediated tumor treatments and offers insights for future development of the field.

IBX-mediated oxidation of unactivated cyclic amines: application in highly diastereoselective oxidative Ugi-type and aza-Friedel-Crafts reactions.

Science.gov (United States)

de Graaff, C; Bensch, L; van Lint, Matthijs J; Ruijter, E; Orru, R V A

2015-10-28

The first o-iodoxybenzoic acid (IBX) mediated oxidation of unactivated amines to imines is described. A range of meso-pyrrolidines were shown to be suitable substrates. The chemical space was further explored with one-pot oxidative Ugi-type and aza-Friedel-Crafts reactions, which proved to be highly diastereoselective.

Ultraselective electrochemiluminescence biosensor based on locked nucleic acid modified toehold-mediated strand displacement reaction and junction-probe.

Science.gov (United States)

Zhang, Xi; Zhang, Jing; Wu, Dongzhi; Liu, Zhijing; Cai, Shuxian; Chen, Mei; Zhao, Yanping; Li, Chunyan; Yang, Huanghao; Chen, Jinghua

2014-12-07

Locked nucleic acid (LNA) is applied in toehold-mediated strand displacement reaction (TMSDR) to develop a junction-probe electrochemiluminescence (ECL) biosensor for single-nucleotide polymorphism (SNP) detection in the BRCA1 gene related to breast cancer. More than 65-fold signal difference can be observed with perfectly matched target sequence to single-base mismatched sequence under the same conditions, indicating good selectivity of the ECL biosensor.

Degradation of sulfadimethoxine catalyzed by laccase with soybean meal extract as natural mediator: Mechanism and reaction pathway.

Science.gov (United States)

Liang, Shangtao; Luo, Qi; Huang, Qingguo

2017-08-01

Natural laccase-mediator systems have been well recognized as an eco-friendly and energy-saving approach in environmental remediation, whose further application is however limited by the high cost of natural mediators and relatively long treatment time span. This study evaluated the water extract of soybean meal, a low-cost compound system, in mediating the laccase catalyzed degradation of a model contaminant of emerging concern, sulfadimethoxine (SDM), and demonstrated it as a promising alternative mediator for soil and water remediation. Removal of 73.3% and 65.6% was achieved in 9 h using soybean meal extract (SBE) as the mediating system for laccase-catalyzed degradation of sulfadimethoxine at the concentration of 1 ppm and 10 ppm, respectively. Further degradation of sulfadimethoxine was observed with multiple SBE additions. Using SBE as mediator increased the 9-h removal of SDM at 1 ppm initial concentration by 52.9%, 49.4%, and 36.3% in comparison to the system mediated by 1-Hydroxybenzotriazole (HBT), p-Coumaric acid (COU) and 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonate) (ABTS), respectively. With the detection of stable coupling products formed with radical scavenger (5,5-Dimethyl-1-pyrroline N-oxide, DMPO), three phenolic compounds (vanillin, apocynin, and daidzein) in SBE were confirmed to serve as mediators for Trametes versicolor laccase. Reaction pathways were proposed based on the results of High Resolution Mass Spectrometry. SO 2 excursion happened during SDM transformation, leading to elimination of antimicrobial activity. Therefore, as a natural, phenol rich, and affordable compound system, the future application of SBE in wastewater and soil remediation is worth exploring. Copyright © 2017 Elsevier Ltd. All rights reserved.

Detonation nanodiamond introduced into samarium doped ceria electrolyte improving performance of solid oxide fuel cell

Science.gov (United States)

Pei, Kai; Li, Hongdong; Zou, Guangtian; Yu, Richeng; Zhao, Haofei; Shen, Xi; Wang, Liying; Song, Yanpeng; Qiu, Dongchao

2017-02-01

A novel electrolyte materials of introducing detonation nanodiamond (DNDs) into samarium doped ceria (SDC) is reported here. 1%wt. DNDs doping SDC (named SDC/ND) can enlarge the electrotyle grain size and change the valence of partial ceria. DNDs provide the widen channel to accelerate the mobility of oxygen ions in electrolyte. Larger grain size means that oxygen ions move easier in electrolyte, it can also reduce the alternating current (AC) impedance spectra of internal grains. The lower valence of partial Ce provides more oxygen vacancies to enhance mobility rate of oxygen ions. Hence all of them enhance the transportation of oxygen ions in SDC/ND electrolyte and the OCV. Ultimately the power density of SOFC can reach 762 mw cm-2 at 800 °C (twice higher than pure SDC, which is 319 mw cm-2 at 800 °C), and it remains high power density in the intermediate temperature (600-800 °C). It is relatively high for the electrolyte supported (300 μm) cells.

Use of dispersive liquid-liquid microextraction for simultaneous preconcentration of samarium, europium, gadolinium and dysprosium

International Nuclear Information System (INIS)

Mallah, M.H.; Atomic Energy Organization of Iran, Tehran; Shemirani, F.; Ghannadi Maragheh, M.

2008-01-01

A new preconcentration method of dispersive liquid-liquid microextraction (DLLME) was developed for simultaneous preconcentration of samarium, europium, gadolinium and dysprosium. DLLME technique was successfully used as a sample preparation method. In this preconcentration method, an appropriate mixture of extraction solvent, disperser solvent was injected rapidly into an aqueous solution containing Sm, Eu, Gd and Dy after complex formation using chelating reagent of the 1-(2-pyridylazo)-2-naphthol (PAN). After phase separation, 0.5 mL of the settled phase containing enriched analytes was determined by inductively coupled plasma optical emission spectrometry (ICP-OES). The main factors affected the preconcentration of Sm, Eu, Gd and Dy were extraction and dispersive solvent type and their volume, extraction time, volume of chelating agent (PAN), centrifuge speed and drying temperature of the samples. Under the best operating condition simultaneous preconcentration factors of 80, 100, 103 and 78 were obtained for Sm, Eu, Gd and Dy, respectively. (author)

Extraction of lanthanide elements and bismuth in molten lithium chloride-liquid bismuth-lithium alloy system

International Nuclear Information System (INIS)

Harada, Makoto; Adachi, Motonari; Kai, Yuichi; Koike, Kenichi

1987-01-01

The equilibrium distributions of neodymium and samarium between molten LiCl and liquid Bi-Li alloy were measured in a wide range of Li-mole fraction in the alloy phase, X Li . These lanthanide elements were extracted through redox reactions. In high X Li range, X Li > 0.03, the distributions of neodymium and bismuth in the salt phase increased markedly. The anomalous increase is attributed to the formation of the compound comprized of Nd, Li, Bi and oxygen in the salt phase. The reaction processes in samarium and neodymium were very fast and the extraction rates are controlled by the diffusion processes of the solutes and metallic lithium. (author)

Basophil histamine release to Amoxicilloyl-poly-L-lysine compared to amoxicillin in patients with IgE-mediated allergic reactions to amoxicillin

DEFF Research Database (Denmark)

Arribas, F; Falkencrone, S; Sola, J

2017-01-01

BACKGROUND: Amoxicillin (AX) is the betalactam most often involved in IgE-mediated reactions and the diagnosis is mainly based on skin testing (ST) although without optimal sensitivity. We have produced a newly AX derivative, amoxicilloyl-poly-L-lysine (APL), and have analysed its IgE recognition...... with AX or APL. Histamine released was determined and expressed as ng of histamine release/mL blood. RESULTS: Patients clinical symptoms were anaphylaxis (N=9), urticaria (N=7), erythema (N=2) and not defined immediate reactions (N=1). The median time interval between reaction and study was 90 days (IQR...

The effect of salmeterol and salbutamol on mediator release and skin responses in immediate and late phase allergic cutaneous reactions

DEFF Research Database (Denmark)

Petersen, Lars Jelstrup; Skov, P S

1999-01-01

on clinical and biochemical EAR and LPR in human skin. METHODS: Measurement of wheal and flare reactions to allergen, codeine, and histamine, and LPR (induration) to allergen. Assessment of histamine and prostaglandin D2 (PGD2) release by microdialysis technique in EAR, and measurement of mediators in LPR......, myeloperoxidase, or eosinophil cationic protein in LPR. CONCLUSIONS: Salmeterol and salbutamol inhibited allergen-induced skin responses, and reduced mediator release in EAR but not LPR. In general, the anti-inflammatory effects of salmeterol did not differ from those induced by salbutamol....

Characterization of luminescent samarium doped HfO2 coatings synthesized by spray pyrolysis technique

International Nuclear Information System (INIS)

Chacon-Roa, C; Guzman-Mendoza, J; Aguilar-Frutis, M; Garcia-Hipolito, M; Alvarez-Fragoso, O; Falcony, C

2008-01-01

Trivalent samarium (Sm 3+ ) doped hafnium oxide (HfO 2 ) films were deposited using the spray pyrolysis deposition technique. The films were deposited on Corning glass substrates at temperatures ranging from 300 to 550 deg. C using chlorides as raw materials. Films, mostly amorphous, were obtained when deposition temperatures were below 350 deg. C. However, for temperatures higher than 400 deg. C, the films became polycrystalline, presenting the HfO 2 monoclinic phase. Scanning electron microscopy of the films revealed a rough surface morphology with spherical particles. Also, electron energy dispersive analysis was performed on these films. The photoluminescence and cathodoluminescence characteristics of the HfO 2 : SmCl 3 films, measured at room temperature, exhibited four main bands centred at 570, 610, 652 and 716 nm, which are due to the well-known intra-4f transitions of the Sm 3+ ion. It was found that the overall emission intensity rose as the deposition temperature was increased. Furthermore, a concentration quenching of the luminescence intensity was also observed

The theoretical basis and clinical methodology for stereotactic interstitial brain tumor irradiation using iododeoxyuridine as a radiation sensitizer and samarium-145 as a brachytherapy source

International Nuclear Information System (INIS)

Goodman, J.H.; Gahbauer, R.A.; Kanellitsas, C.; Clendenon, N.R.; Laster, B.H.; Fairchild, R.G.

1989-01-01

High grade astrocytomas have proven resistant to all conventional therapy. A technique to produce radiation enhancement during interstitial brain tumor irradiation by using a radiation sensitizer (IdUrd) and by stimulation of Auger electron cascades through absorption of low energy photons in iodine (Photon activation) is described. Clinical studies using IdUrd, 192 Ir as a brachytherapy source, and external radiation have produced promising results. Substituting samarium-145 for 192 Ir in this protocol is expected to produce enhanced results. 15 refs

Physiological and cognitive mediators for the association between self-reported depressed mood and impaired choice stepping reaction time in older people.

NARCIS (Netherlands)

Kvelde, T.; Pijnappels, M.A.G.M.; Delbaere, K.; Close, J.C.; Lord, S.R.

2010-01-01

Background. The aim of the study was to use path analysis to test a theoretical model proposing that the relationship between self-reported depressed mood and choice stepping reaction time (CSRT) is mediated by psychoactive medication use, physiological performance, and cognitive ability.A total of

Report on thermic effects in the study of the control and propagation of nuclear reactions

International Nuclear Information System (INIS)

Naudet, R.

It is very likely that nuclear reactions in natural reactors are governed by temperature, chiefly as a result of the moderation rate when the water density is altered. Since reactors operate under high pressure, with supercritical water, high temperatures (at least 350 to 400 0 C in some instances) are required in order to stabilize the reactors. Some typical calculations are shown in order to illustrate the changes in the control temperature during irradiation. The speed and, therefore, the duration of reactions is determined by the need to maintain the necessary temperature required for criticality, with heat dissipation conditions taken into account. Apparent measured durations are compatible with heat dissipation by simple conduction. However, it is likely that convection currents exist, and that their effects are superimposed on those of simple conduction. Reaction propagation must also be taken into consideration since criticality cannot be realized simultaneously at every point. The presence of impurities such as gadolinium or samarium in the mineral ore allows reactions to propagate in initially subcritical increments, through progressive breakdown of the impurities by means of neutronic diffusion. However, it has been shown that this phenomenon is seriously affected by thermic effects. Typical calculations are presented. Results clearly depend on temperature distribution hypotheses; sufficient thermic coupling can totally inhibit reaction propagation. It is concluded that, if convection currents are present, propagation is favored inversely with respect to the currents, and therefore a priori downstream of the reactors. 6 figures

Results after therapy of pain from bone metastases with Samarium-153 in our centers in Lima, Peru

International Nuclear Information System (INIS)

Alvarado, N.; Eskenazi, S.; Valle, M.P.; Montoya, J.; Castro, M.; Montiel, L.; Velarde, V.; Jauregui, I.; Cueto, C.

2004-01-01

Full text: 105 patients with bone metastases from prostate and breast cancer; between 42 and 78 years age (median 61 years) were evaluated. Patients had intense pain that could not be managed with combinations of analgesic and anti tumoral drugs. All patients received 1.2 mCi/kg of Samarium-153 intravenously as treatment for pain due to bony metastases. The isotope obtained from atomic reactor placed in Lima - Peru, was provided by Peruvian Nuclear Energy Institute (IPEN). One week before therapy, all the patients had a bone scan study with Tc99m-MDP that showed the presence of multiple bone metastases with high blastic activity. Haematology and biochemical parameter checked were: Creatinine ( 150,000 mm3), Leukocytes (> 5,000 mm3), Red cells (>3,500,000 mm3). No problems were encountered during intravenous administration of the radioisotope. The side effects after treatment were: Primary effects: 16 cases of nausea, 2 of vomiting, 3 of headache, 28 had increment of pain, 6 had flushing. 50 patients did not have the primary symptoms. Secondary effects: 3 Patients showed drop in leukocyte count between 2nd and 3rd week of therapy. Red cells showed 10-15% decrease between 6th to 8th week. Platelets showed a decrease of about 15% with one peak between 1st and 2nd week post Samarium therapy. Data was analysed using an analogue visual scale of the pain with values from 0 - 10 (0-no pain; 10-maximum pain) and in the same way using the E.C.O.G. scale (Eastern Cooperative Oncology Group) in relationship with the Karnofsky index in order to establish functional recovery for each patient. The decrease of pain was seen between 4th-7th days (average 8 days). A second dose was given after 60 days in 12 patients and a third dose in 3 cases.11 patients died due to different causes between 30 - 60 days post treatment. The analgesic dose came down significantly in 80% of patients. We conclude that palliative therapy of metastatic bone pain in Peru is possible with radionuclides. It

Current rectification by mediating electroactive polymers

Energy Technology Data Exchange (ETDEWEB)

Ybarra, Gabriel; Moina, Carlos [Centro de Investigacion sobre Electrodeposicion y Procesos Superficiales, Instituto Nacional de Tecnologia Industrial, CC 157, (1650) San Martin (Argentina); Florit, M. Ines [INIFTA, Facultad de Ciencias Exactas, UNLP, Suc. 4, CC 16, (1900) La Plata (Argentina); Posadas, Dionisio [INIFTA, Facultad de Ciencias Exactas, UNLP, Suc. 4, CC 16, (1900) La Plata (Argentina)], E-mail: dposadas@inifta.unlp.edu.ar

2008-04-20

In this work we briefly review the theoretical basis for the electrochemical rectification in mediated redox reactions at redox polymer modified electrodes. Electrochemical rectification may have two distinct origins. It is either caused by a slow kinetics of the reaction between the external redox couple and the mediator or it is originated by a slow electronic transport within the film under an unfavorable thermodynamic condition. We show experimental results for the redox mediation reaction of poly(o-aminophenol) (POAP) on the Fe{sup 2+/3+} and on the Fe(CN){sub 6}{sup 3-/4-} redox couples in solution that prove the proposed mechanisms of electrochemical rectification.

Current rectification by mediating electroactive polymers

International Nuclear Information System (INIS)

Ybarra, Gabriel; Moina, Carlos; Florit, M. Ines; Posadas, Dionisio

2008-01-01

In this work we briefly review the theoretical basis for the electrochemical rectification in mediated redox reactions at redox polymer modified electrodes. Electrochemical rectification may have two distinct origins. It is either caused by a slow kinetics of the reaction between the external redox couple and the mediator or it is originated by a slow electronic transport within the film under an unfavorable thermodynamic condition. We show experimental results for the redox mediation reaction of poly(o-aminophenol) (POAP) on the Fe 2+/3+ and on the Fe(CN) 6 3-/4- redox couples in solution that prove the proposed mechanisms of electrochemical rectification

On the effects of pressure and irradiation on the transport properties of samarium compounds with unstable valence

International Nuclear Information System (INIS)

Morillo, J.

1983-06-01

We present the first extensive study of electronic transport properties of ''quasi-stoichiometric'' SmS as a function of pressure P, temperature T, magnetic field B and defect concentration C. SmS which is a semiconductor, undergoes with increasing P a first order transition towards an homogeneous intermediate valence state. In the semiconducting phase (s.c.), the energie epsilon(f) necessary to delocalize a 4f electron increases greatly with T and is about 250meV at 300K. The phase diagram for the first order electronic transition Sm 2 + →Smsup(2+epsilon) with P has been determined for T 6 has been investigated by resistivity measurements under irradiation at 21K. The threshold energy Ed for displacement of Sm in SmS has been determined: Ed(Sm) = 20 +- 2 eV, and the observed effects of irradiation have been associated to samarium displacements (vacancies and interstitials) [fr

Effect of Zinc Oxide Doping on Electroluminescence and Electrical Behavior of Metalloporphyrins-Doped Samarium Complex

Science.gov (United States)

Janghouri, Mohammad; Amini, Mostafa M.

2018-02-01

Samarium complex [(Sm(III)] as a new host material was used for preparation of red organic light-emitting diodes (OLEDs). Devices with configurations of indium-doped tin oxide (ITO)/poly(3,4-ethylenedioxythiophene):(poly(styrenesulfonate) (PEDOT:PSS (50 nm)/polyvinyl carbazole (PVK):[zinc oxide (ZnO)] (50 nm)/[(Sm(III)]:[zinc(II) 2,3-tetrakis(dihydroxyphenyl)-porphyrin and Pt(II) 2,3-dimethoxyporphyrin] (60 nm)/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) (15 nm)/Al (150 nm) have been fabricated and investigated. An electroplex occurring at the (PVK/Sm: Pt(II) 2,3-dimethoxyporphyrin) interface has been suggested when ZnO nanoparticles were doped in PVK. OLED studies have revealed that the photophysical characteristics and electrical behavior of devices with ZnO nanoparticles are much better than those of devices with pure PVK. The efficiency of devices based on [(Sm(III)] was superior than that of known aluminum tris(8-hydroxyquinoline) (Alq3) and also our earlier reports on red OLEDs under the same conditions.

Ex Vivo Antioxidant Activity of Selected Medicinal Plants against Fenton Reaction-Mediated Oxidation of Biological Lipid Substrates

Directory of Open Access Journals (Sweden)

Namratha Pai Kotebagilu

2015-01-01

Full Text Available Free radical-mediated oxidation is often linked to various degenerative diseases. Biological substrates with lipids as major components are susceptible to oxygen-derived lipid peroxidation due to their composition. Lipid peroxide products act as biomarkers in evaluating the antioxidant potential of various plants and functional foods. The study focused on evaluation of the antioxidant potential of two extracts (methanol and 80% methanol of four medicinal plants, Andrographis paniculata, Costus speciosus, Canthium parviflorum, and Abrus precatorius, against Fenton reaction-mediated oxidation of three biological lipid substrates; cholesterol, low-density lipoprotein, and brain homogenate. The antioxidant activity of the extracts was measured by thiobarbituric acid reactive substances method. Also, the correlation between the polyphenol, flavonoid content, and the antioxidant activity in biological substrates was analyzed. Results indicated highest antioxidant potential by 80% methanol extract of Canthium parviflorum (97.55%, methanol extract of Andrographis paniculata (72.15%, and methanol extract of Canthium parviflorum (49.55% in cholesterol, low-density lipoprotein, and brain, respectively. The polyphenol and flavonoid contents of methanol extract of Andrographis paniculata in cholesterol (r=0.816 and low-density lipoprotein (r=0.948 and Costus speciosus in brain (r=0.977, polyphenols, and r=0.949, flavonoids correlated well with the antioxidant activity. The findings prove the antioxidant potential of the selected medicinal plants against Fenton reaction in biological lipid substrates.

Biodistribution of samarium-153-EDTMP in rats treated with docetaxel Biodistribuição de EDTMP-153-samário em ratos tratados com docetaxel

Directory of Open Access Journals (Sweden)

Arthur Villarim Neto

2009-02-01

Full Text Available PURPOSE: Many patients with metastatic bone disease have to use radiopharmaceuticals associated with chemotherapy to relieve bone pain. The aim of this study was to assess the influence of docetaxel on the biodistribution of samarium-153-EDTMP in bones and other organs of rats. METHODS: Wistar male rats were randomly allocated into 2 groups of 6 rats each. The DS (docetaxel/samarium group received docetaxel (15 mg/kg intraperitoneally in two cycles 11 days apart. The S (samarium/control group rats were not treated with docetaxel. Nine days after chemotherapy, all the rats were injected with 0.1ml of samarium-153-EDTMP via orbital plexus (25µCi. After 2 hours, the animals were killed and samples of the brain, thyroid, lung, heart, stomach, colon, liver, kidney and both femurs were removed. The percentage radioactivity of each sample (% ATI/g was determined in an automatic gamma-counter (Wizard-1470, Perkin-Elmer, Finland. RESULTS: On the 9th day after the administration of the 2nd chemotherapy cycle, the rats had a significant weight loss (314.50±22.09g compared (pOBJETIVO: Muitos pacientes com metástases ósseas são tratados com radiofármacos associados com quimioterapia para alívio da dor óssea. O objetivo do trabalho foi estudar a influência do docetaxel na biodistribuição do EDTMP-153-samário nos ossos e outros órgãos de ratos. MÉTODOS: Ratos Wistar foram aleatoriamente alocados em 2 grupos de 6 animais cada. O grupo DS (docetaxel/samário recebeu docetaxel (15 mg/kg intraperitoneal em dois ciclos com 11 dias de intervalo. Os ratos do grupo S (samário/controle não foram tratados com docetaxel. Nove dias após a quimioterapia, todos os animais receberam 0,1ml de EDTMP-153-samário via plexo orbital (25µCi. Após 2 horas, os animais foram mortos e feitas biópsias de cérebro, tireóide, pulmão, coração, estômago, cólon, fígado, rim e fêmures. O percentual de radioatividade por grama (%ATI/g de tecido de cada bi

Copper-Mediated Reactions of Nitriles with Nitromethanes: Aza-Henry Reactions and Nitrile Hydrations.

Science.gov (United States)

Kuwabara, Jun; Sawada, Yoshiharu; Yoshimatsu, Mitsuhiro

2018-02-16

In this study, the first aza-Henry reaction of nitriles with nitromethane in a CuI/Cs 2 CO 3 /DBU system is described. The process was conveniently and directly used for the synthesis of β-aminonitroalkenes 2a-x and tolerated aryl-, alkyl-, hetaryl-, alkenyl-, and alkynylnitriles. The resulting aminonitroalkenes 2 could be successfully transformed to the corresponding 2-nitroacetophenones, 2-amino-1-halonitroalkenes, 2-alkylaminonitroalkenes, or 3-nitropyridines. In the presence of H 2 O, the aza-Henry reaction turned the reaction path to the nitrile hydration to exclusively yield the amides 3a-s.

The Oklo natural nuclear reactors: neutron parameters, age and duration of the reactions, uranium and fission products migrations

International Nuclear Information System (INIS)

Ruffenach, J.-C.

1979-09-01

Mass spectrometry and isotopic dilution technique are used in order to carry out, on various samples from the fossil nuclear reactors at Oklo, Gabon, isotopic and chemical analyses of some particular elements involved in the nuclear reactions: uranium, lead, bismuth, thorium, rare gases (krypton, xenon), rare earths (neodymium, samarium, europium, gadolinium, dysprosium), ruthenium and palladium. Interpretations of these analyses lead to the determination of many neutron parameters such as the neutron fluence received by the samples, the spectrum index, the conversion coefficient, and also the percentages of fissions due to uranium-238 and plutonium-239 and the total number of fissions relative to uranium. All these results make it possible to determine the age of the nuclear reactions by measuring the amounts of fission rare earths formed, i.e. 1.97 billion years. This study brings some informations to the general problem of radioactive wastes storage in deep geological formations, the storage of uranium, plutonium and many fission products having been carried out naturally, and for about two billion years [fr

Developmental endothelial locus-1 modulates platelet-monocyte interactions and instant blood-mediated inflammatory reaction in islet transplantation.

Science.gov (United States)

Kourtzelis, Ioannis; Kotlabova, Klara; Lim, Jong-Hyung; Mitroulis, Ioannis; Ferreira, Anaisa; Chen, Lan-Sun; Gercken, Bettina; Steffen, Anja; Kemter, Elisabeth; Klotzsche-von Ameln, Anne; Waskow, Claudia; Hosur, Kavita; Chatzigeorgiou, Antonios; Ludwig, Barbara; Wolf, Eckhard; Hajishengallis, George; Chavakis, Triantafyllos

2016-04-01

Platelet-monocyte interactions are strongly implicated in thrombo-inflammatory injury by actively contributing to intravascular inflammation, leukocyte recruitment to inflamed sites, and the amplification of the procoagulant response. Instant blood-mediated inflammatory reaction (IBMIR) represents thrombo-inflammatory injury elicited upon pancreatic islet transplantation (islet-Tx), thereby dramatically affecting transplant survival and function. Developmental endothelial locus-1 (Del-1) is a functionally versatile endothelial cell-derived homeostatic factor with anti-inflammatory properties, but its potential role in IBMIR has not been previously addressed. Here, we establish Del-1 as a novel inhibitor of IBMIR using a whole blood-islet model and a syngeneic murine transplantation model. Indeed, Del-1 pre-treatment of blood before addition of islets diminished coagulation activation and islet damage as assessed by C-peptide release. Consistently, intraportal islet-Tx in transgenic mice with endothelial cell-specific overexpression of Del-1 resulted in a marked decrease of monocytes and platelet-monocyte aggregates in the transplanted tissues, relative to those in wild-type recipients. Mechanistically, Del-1 decreased platelet-monocyte aggregate formation, by specifically blocking the interaction between monocyte Mac-1-integrin and platelet GPIb. Our findings reveal a hitherto unknown role of Del-1 in the regulation of platelet-monocyte interplay and the subsequent heterotypic aggregate formation in the context of IBMIR. Therefore, Del-1 may represent a novel approach to prevent or mitigate the adverse reactions mediated through thrombo-inflammatory pathways in islet-Tx and perhaps other inflammatory disorders involving platelet-leukocyte aggregate formation.

Metal-catalyzed asymmetric aldol reactions

Energy Technology Data Exchange (ETDEWEB)

Dias, Luiz C.; Lucca Junior, Emilio C. de; Ferreira, Marco A. B.; Polo, Ellen C., E-mail: ldias@iqm.unicamp.br [Universidade de Campinas (UNICAMP), SP (Brazil). Inst. de Quimica

2012-12-15

The aldol reaction is one of the most powerful and versatile methods for the construction of C-C bonds. Traditionally, this reaction was developed in a stoichiometric version; however, great efforts in the development of chiral catalysts for aldol reactions were performed in recent years. Thus, in this review article, the development of metal-mediated chiral catalysts in Mukaiyama-type aldol reaction, reductive aldol reaction and direct aldol reaction are discussed. Moreover, the application of these catalysts in the total synthesis of complex molecules is discussed. (author)

1,5-Asymmetric induction in the boron-mediated aldol reaction of β-oxygenated methyl ketones

International Nuclear Information System (INIS)

Dias, Luiz C.

2007-01-01

High levels of substrate-based 1,5-stereo induction are obtained in the boron-mediated aldol reactions of β-oxygenated methyl ketones with achiral and chiral aldehydes. Remote induction from the boron enolates gives the 1,5-anti adducts, with the enolate pi-facial selectivity critically dependent upon the nature of the beta-alkoxy protecting group. This 1,5-anti aldol methodology has been strategically employed in the total synthesis of several natural products. At present, the origin of the high level of 1,5-anti induction obtained with the boron enolates is unclear, although a model based on a hydrogen bonding between the alkoxy oxygen and the formyl hydrogen has been recently proposed. (author)

Considering a Threshold Energy in Reactive Transport Modeling of Microbially Mediated Redox Reactions in an Arsenic-Affected Aquifer

Directory of Open Access Journals (Sweden)

Marco Rotiroti

2018-01-01

Full Text Available The reductive dissolution of Fe-oxide driven by organic matter oxidation is the primary mechanism accepted for As mobilization in several alluvial aquifers. These processes are often mediated by microorganisms that require a minimum Gibbs energy available to conduct the reaction in order to sustain their life functions. Implementing this threshold energy in reactive transport modeling is rarely used in the existing literature. This work presents a 1D reactive transport modeling of As mobilization by the reductive dissolution of Fe-oxide and subsequent immobilization by co-precipitation in iron sulfides considering a threshold energy for the following terminal electron accepting processes: (a Fe-oxide reduction, (b sulfate reduction, and (c methanogenesis. The model is then extended by implementing a threshold energy on both reaction directions for the redox reaction pairs Fe(III reduction/Fe(II oxidation and methanogenesis/methane oxidation. The optimal threshold energy fitted in 4.50, 3.76, and 1.60 kJ/mol e− for sulfate reduction, Fe(III reduction/Fe(II oxidation, and methanogenesis/methane oxidation, respectively. The use of models implementing bidirectional threshold energy is needed when a redox reaction pair can be transported between domains with different redox potentials. This may often occur in 2D or 3D simulations.

Development and evaluation of copper-67 and samarium-153 labeled conjugates for tumor radioimmunotherapy

International Nuclear Information System (INIS)

Srivastava, S.C.; Mausner, L.F.; Mease, R.C.; Meinken, G.E.; Joshi, V.; Kolsky, K.; Sweet, M.; Steplewski, Z.

1995-01-01

The potential of utilizing receptor-specific agents such as monoclonal antibodies (MAb), and MAb-derived smaller molecules, as carriers of radionuclides for the selective destruction of tumors has stimulated much research activity. The success of such applications depends on many factors, especially the tumor binding properties of the antibody reagent, the efficiency of labeling and in-vivo stability of the radioconjugate and, on the careful choice of the radionuclide best suited to treat the tumor under consideration. The radiolabeled antibody technique for radioimmunotherapy (RIT), however, has experienced many limitations, and its success has not matched the expectations that were raised more than a decade ago. The problems that have been identified include: (i) degradation of antibody immunoreactivity resulting from chemical manipulations required for labeling; (ii) lack of suitable radioisotopes and methods for stable attachment of the radiolabel; (iii) in-vivo instability of the radioimmunoconjugates; (iv) excessive accumulation of activity in non-target locations; and (v) lack of radioimmunoconjugate accessibility to cells internal to a tumor mass. A careful choice of the radionuclide(s) best suited to treat the tumor under consideration is one of the most important requirements for successful radioimmunotherapy. This study evaluates copper 67 and samarium 153 for tumor radioimmunotherapy

Polyarene mediators for mediated redox flow battery

Science.gov (United States)

Delnick, Frank M.; Ingersoll, David; Liang, Chengdu

2018-01-02

The fundamental charge storage mechanisms in a number of currently studied high energy redox couples are based on intercalation, conversion, or displacement reactions. With exception to certain metal-air chemistries, most often the active redox materials are stored physically in the electrochemical cell stack thereby lowering the practical gravimetric and volumetric energy density as a tradeoff to achieve reasonable power density. In a general embodiment, a mediated redox flow battery includes a series of secondary organic molecules that form highly reduced anionic radicals as reaction mediator pairs for the reduction and oxidation of primary high capacity redox species ex situ from the electrochemical cell stack. Arenes are reduced to stable anionic radicals that in turn reduce a primary anode to the charged state. The primary anode is then discharged using a second lower potential (more positive) arene. Compatible separators and solvents are also disclosed herein.

Mechanism of the Suzuki–Miyaura Cross-Coupling Reaction Mediated by [Pd(NHC)(allyl)Cl] Precatalysts

KAUST Repository

Meconi, Giulia Magi

2017-05-24

Density functional theory calculations have been used to investigate the activation mechanism for the precatalyst series [Pd]-X-1–4 derived from [Pd(IPr)(R-allyl)X] species by substitutions at the terminal position of the allyl moiety ([Pd] = Pd(IPr); R = H (1), Me (2), gem-Me2 (3), Ph (4), X = Cl, Br). Next, we have investigated the Suzuki–Miyaura cross-coupling reaction for the active catalyst species IPr-Pd(0) using 4-chlorotoluene and phenylboronic acid as substrates and isopropyl alcohol as a solvent. Our theoretical findings predict an upper barrier trend, corresponding to the activation mechanism for the [Pd]-Cl-1–4 series, in good agreement with the experiments. They indeed provide a quantitative explanation of the low yield (12%) displayed by [Pd]-Cl-1 species (ΔG⧧ ≈ 30.0 kcal/mol) and of the high yields (≈90%) observed in the case of [Pd]-Cl-2–4 complexes (ΔG⧧ ≈ 20.0 kcal/mol). Additionally, the studied Suzuki–Miyaura reaction involving the IPr-Pd(0) species is calculated to be thermodynamically favorable and kinetically facile. Similar investigations for the [Pd]-Br-1–4 series, derived from [Pd(IPr)(R-allyl)Br], indicate that the oxidative addition step for IPr-Pd(0)-mediated catalysis with 4-bromotoluene is kinetically more favored than that with 4-chlorotoluene. Finally, we have explored the potential of Ni-based complexes [Ni((IPr)(R-allyl)X] (X = Cl, Br) as Suzuki–Miyaura reaction catalysts. Apart from a less endergonic reaction energy profile for both precatalyst activation and catalytic cycle, a steep increase in the predicted upper energy barriers (by 2.0–15.0 kcal/mol) is calculated in the activation mechanism for the [Ni]-X-1–4 series compared to the [Pd]-X-1–4 series. Overall, these results suggest that Ni-based precatalysts are expected to be less active than the Pd-based precatalysts for the studied Suzuki–Miyaura reaction.

Vaporization of Samarium trichloride studied by thermogravimetry

International Nuclear Information System (INIS)

Esquivel, Marcelo R.; Pasquevich, Daniel M.

2003-01-01

In the present work, the vaporization reaction of SmCl 3 (l) obtained from the 'in situ' reaction of Sm 2 O 3 (s) and Cl 2 (g)-C(s) was studied by thermogravimetry under controlled atmosphere. The effects of both the temperature between 825 C degrees and 950 C degrees and the total flow gas on the vaporization rate of the following reaction: SmCl 3 (l) = SmCl 3 (g) were analyzed. The vaporization rate of the process was found to be independent of then total gas flow rate and highly dependent on the temperature. E ap calculation led to a value of 240 ± 10 kJ.mol -1 . A comparison between this value and that of the molar enthalpy of vaporization allow to the conclusion that the reaction occur in conditions near to equilibrium. The SmCl 3 identity was determined by X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS). (author)

Optimization of Si–C reaction temperature and Ge thickness in C-mediated Ge dot formation

Energy Technology Data Exchange (ETDEWEB)

Satoh, Yuhki, E-mail: yu-ki@ecei.tohoku.ac.jp; Itoh, Yuhki; Kawashima, Tomoyuki; Washio, Katsuyoshi

2016-03-01

To form Ge dots on a Si substrate, the effect of thermal reaction temperature of sub-monolayer C with Si (100) was investigated and the deposited Ge thickness was optimized. The samples were prepared by solid-source molecular beam epitaxy with an electron-beam gun for C sublimation and a Knudsen cell for Ge evaporation. C of 0.25 ML was deposited on Si (100) at a substrate temperature of 200 °C, followed by a high-temperature treatment at the reaction temperature (T{sub R}) of 650–1000 °C to create Si–C bonds. Ge equivalent to 2 to 5 nm thick was subsequently deposited at 550 °C. Small and dense dots were obtained for T{sub R} = 750 °C but the dot density decreased and the dot diameter varied widely in the case of lower and higher T{sub R}. A dot density of about 2 × 10{sup 10} cm{sup −2} was achieved for Ge deposition equivalent to 3 to 5 nm thick and a standard deviation of dot diameter was the lowest of 10 nm for 5 nm thick Ge. These results mean that C-mediated Ge dot formation was strongly influenced not only by the c(4 × 4) reconstruction condition through the Si–C reaction but also the relationship between the Ge deposition thickness and the exposed Si (100)-(2 × 1) surface area. - Highlights: • The effect of Si–C reaction temperature on Ge dot formation was investigated. • Small and dense dots were obtained for T{sub R} = 750 °C. • The dot density of about 2 × 10{sup 10} cm{sup −2} was achieved for Ge = 3 to 5 nm. • The standard deviation of dot diameter was the lowest of 10 nm at Ge = 5 nm.

Laccase mediated transformation of 17β-estradiol in soil

International Nuclear Information System (INIS)

Singh, Rashmi; Cabrera, Miguel L.; Radcliffe, David E.; Zhang, Hao; Huang, Qingguo

2015-01-01

It is known that 17β-estradiol (E2) can be transformed by reactions mediated by some oxidoreductases such as laccase in water. Whether or how such reactions can happen in soil is however unknown although they may significantly impact the environmental fate of E2 that is introduced to soil by land application of animal wastes. We herein studied the reaction of E2 in a model soil mediated by laccase, and found that the reaction behaviors differ significantly from those in water partly because of the dramatic difference in laccase stability. We also examined E2 transformation in soil using 14 C-labeling in combination with soil organic matter extraction and size exclusion chromatography, which indicated that applied 14 C radioactivity was preferably bound to humic acids. The study provides useful information for understanding the environmental fate of E2 and for developing a novel soil remediation strategy via enzyme-enhanced humification reactions. - Highlights: • E2 was effectively transformed in soil through reactions mediated by laccase. • The reaction behaviors in soil differ significantly from those in water. • E2 was preferably bound to the humic acids in soil. • Laccase treatment resulted in changes in the structures of the humic acids. - E2 was effectively transformed in soil by preferably binding to the humic acids through reactions mediated by laccase

Coprecipitation experiment with Sm hydroxide using a multitracer produced by nuclear spallation reaction: A tool for chemical studies with superheavy elements

International Nuclear Information System (INIS)

Kasamatsu, Yoshitaka; Yokokita, Takuya; Toyomura, Keigo; Shigekawa, Yudai; Haba, Hiromitsu; Kanaya, Jumpei; Huang, Minghui; Ezaki, Yutaka; Yoshimura, Takashi; Morita, Kosuke; Shinohara, Atsushi

2016-01-01

To establish a new methodology for superheavy element chemistry, the coprecipitation behaviors of 34 elements with samarium hydroxide were investigated using multitracer produced by a spallation of Ta. The chemical reactions were rapidly equilibrated within 10 s for many elements. In addition, these elements exhibited individual coprecipitation behaviors, and the behaviors were qualitatively related to their hydroxide precipitation behaviors. It was demonstrated that the ammine and hydroxide complex formations of superheavy elements could be investigated using the established method. - Highlights: • We established a new methodology for superheavy element (SHE) chemistry. • Coprecipitation behaviors of 34 elements with Sm hydroxide could be simultaneously investigated by using multitracer. • The complex formations were investigated from the coprecipitation behaviors. • The established method will lead to the study on various precipitates of SHEs.

Possible self-complexity and affective reactions to goal-relevant evaluation.

Science.gov (United States)

Niedenthal, P M; Setterlund, M B; Wherry, M B

1992-07-01

The complexity of people's self-concept appears to be inversely related to the intensity of their reactions to evaluative feedback about present goals and abilities (Linville, 1985, 1987). The idea that the complexity of individuals' possible self-concept similarly mediates reactions to feedback regarding future goals was investigated. Two preliminary studies suggested that complexity of the actual self only explains 20% to 30% of the variance in possible self-complexity. Three studies were conducted. Support was found for the idea that possible self-complexity mediates affective reactions to evaluative feedback about future goals and actual self-complexity mediates affective reactions to evaluative feedback about present goals. The findings underscore the independent roles of the organization of actual and possible self-concepts in affective processes.

An estimation of influence of humic acid and organic matter originated from bentonite on samarium solubility

International Nuclear Information System (INIS)

Kanaji, Mariko; Sato, Haruo; Sasahira, Akira

1999-10-01

Organic acids in groundwater are considered to form complexes and increase the solubility of radionuclides released from vitrified waste in a high-level radioactive waste (HLW) repository. To investigate whether the solubility of samarium (Sm) is influenced by organic substances, we measured Sm solubility in the presence of different organic substances and compared those values with results from thermodynamic predictions. Humic acid (Aldrich) is commercially available and soluble organic matter originated from bentonite were used as organic substances in this study. Consequently, the solubility of Sm showed a tendency to apparently increase with increasing the concentration of humic acid, but in the presence of carbonate, thermodynamic predictions suggested that the dominant species are carbonate complexes and that the effect of organic substances are less than that of carbonate. Based on total organic carbon (TOC), the increase of Sm solubility measured with humic acid (Aldrich) was more significant than that in the case with soluble organic matter originated from bentonite. Since bentonite is presumed to include also simple organic matters of which stability constant for forming complexes is low, the effect of soluble organic matter originated from bentonite on the solubility of Sm is considered to be less effective than that of humic acid (Aldrich). Experimental values were compared with model prediction, proposed by Kim, based on data measured in a low pH region. Tentatively we calculated the increase in Sm solubility assuming complexation with humic acid. Trial calculations were carried out on the premise that the complexation reaction of metal ion with humic acid is based on neutralization process by 1-1 complexation. In this process, it was assumed that one metal ion coordinates with one unit of complexation sites which number of proton exchange sites is equal to ionic charge. Consequently, Kim's model indicated that carbonate complexes should be dominant

Optimization of the THP-1 activation assay to detect pharmaceuticals with potential to cause immune mediated drug reactions.

Science.gov (United States)

Corti, Daniele; Galbiati, Valentina; Gatti, Nicolò; Marinovich, Marina; Galli, Corrado L; Corsini, Emanuela

2015-10-01

Despite important impacts of systemic hypersensitivity induced by pharmaceuticals, for such endpoint no reliable preclinical approaches are available. We previously established an in vitro test to identify contact and respiratory allergens based on interleukin-8 (IL-8) production in THP-1 cells. Here, we challenged it for identification of pharmaceuticals associated with systemic hypersensitivity reactions, with the idea that drug sensitizers share common mechanisms of cell activation. Cells were exposed to drugs associated with systemic hypersensitivity reactions (streptozotocin, sulfamethoxazole, neomycin, probenecid, clonidine, procainamide, ofloxacin, methyl salicylate), while metformin was used as negative drug. Differently to chemicals, drugs tested were well tolerated, except clonidine and probenecid, with no signs of cytotoxicity up to 1-2mg/ml. THP-1 activation assay was adjusted, and conditions, that allow identification of all sensitizing drugs tested, were established. Next, using streptozotocin and selective inhibitors of PKC-β and p38 MAPK, two pathways involved in chemical allergen-induced cell activation, we tested the hypothesis that similar pathways were also involved in drug-induced IL-8 production and CD86 upregulation. Results indicated that drugs and chemical allergens share similar activation pathways. Finally, we made a structure-activity hypothesis related to hypersensitivity reactions, trying to individuate structural requisite that can be involved in immune mediated adverse reactions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Immunological aspects of nonimmediate reactions to beta-lactam antibiotics.

Science.gov (United States)

Rodilla, Esther Morena; González, Ignacio Dávila; Yges, Elena Laffond; Bellido, Francisco Javier Múñoz; Bara, María Teresa Gracia; Toledano, Félix Lorente

2010-09-01

beta-lactam antibiotics are the agents most frequently implied in immune drug adverse reactions. These can be classified as immediate or nonimmediate according to the time interval between the last drug administration and their onset. Mechanisms of immediate IgE-mediated reactions are widely studied and are therefore better understood. Nonimmediate reactions include a broad number of clinical entities like mild maculopapular exanthemas, the most common, and other less frequent but more severe reactions such as Stevens-Johnson syndrome, toxic epidermal necrolysis, acute exanthematic pustulosis or cytopenias. These nonimmediate reactions are mainly mediated by T cells but the precise underlying mechanisms are not well elucidated. This fact complicates the allergological evaluation of patients with this type of reaction and available tests have demonstrated poor sensitivity and specificity.

"Assault-related shame mediates the association between negative social reactions to disclosure of sexual assault and psychological distress": Correction to Decou et al. (2017).

Science.gov (United States)

2018-03-01

Reports an error in "Assault-related shame mediates the association between negative social reactions to disclosure of sexual assault and psychological distress" by Christopher R. DeCou, Trevor T. Cole, Shannon M. Lynch, Maria M. Wong and Kathleen C. Matthews ( Psychological Trauma: Theory, Research, Practice, and Policy , 2017[Mar], Vol 9[2], 166-172). In the article, there was an error in the coding of missing values thus effecting the abstract, Methods, Results, and Discussion sections. The frequency counts for sexual assault victimization, reactions to social disclosure, and assault-related shame were calculated incorrectly due to an error in the coding of missing values, and have been corrected in the description of participants and in the results and discussion sections. In addition, the sample size was incorrectly reported as N = 207, and should have appeared as "N = 208." The sample size and corresponding percentages have been corrected throughout the text. Two transcription errors for the indirect effects via PTSD and global distress were also corrected. These indirect effects were incorrectly reported as "PCL-C; β = .27," and "OQ-45.2;β = .21," and should have appeared as "PCL-C;β = .26," and "OQ-45.2; β = .20." (The following abstract of the original article appeared in record 2016-43136-001.) Objective: Several studies have identified associations between social reactions to disclosure of sexual assault and psychological distress; however, no studies have evaluated shame as a mediator of this association. This study evaluated assault-related shame as a mediator of the associations between negative social reactions to disclosure of sexual assault and symptoms of posttraumatic stress disorder (PTSD), depression, and global distress and hypothesized that there would be an indirect effect of social reactions to disclosure upon symptoms of psychopathology via assault-related shame. Participants were 207 female psychology undergraduates who reported past

Study of samarium modified lead zirconate titanate and nickel zinc ferrite composite system

Energy Technology Data Exchange (ETDEWEB)

Rani, Rekha [Department of Physics, SD PG College, Panipat 132103 (India); School of Physics and Materials Science, Thapar University, Patiala 147004 (India); Juneja, J.K., E-mail: jk_juneja@yahoo.com [Department of Physics, Hindu College, Sonepat 131001 (India); Singh, Sangeeta [Department of Physics, GVM Girls College, Sonepat 131001 (India); Raina, K.K. [School of Physics and Materials Science, Thapar University, Patiala 147004 (India); Prakash, Chandra [Solid State Physics Laboratory, Timarpur, Delhi 110054 (India)

2015-03-15

In the present work, composites of samarium substituted lead zirconate titanate and nickel zinc ferrite with compositional formula 0.95Pb{sub 1−3x/2} Sm{sub x}Zr{sub 0.65}Ti{sub 0.35}O{sub 3}–0.05Ni{sub 0.8}Zn{sub 0.2}Fe{sub 2}O{sub 4} (x=0, 0.01, 0.02 and 0.03) were prepared by the conventional solid state route. X-ray diffraction analysis was carried out to confirm the coexistence of individual phases. Microstructural study was done by using scanning electron microscope. Dielectric constant and loss were studied as a function of temperature and frequency. To study ferroelectric and magnetic properties of the composite samples, corresponding P–E and M–H hysteresis loops were recorded. Change in magnetic properties of electrically poled composite sample (x=0.02) was studied to confirm the magnetoelectric (ME) coupling. ME coefficient (dE/dH) of the samples (x=0 and 0.02) was measured as a function of DC magnetic field. - Highlights: • We are reporting the effect of Sm substitution on PZT–NiZn ferrite composites. • Observation of both P–E and M–H loops confirms ferroelectric and magnetic ordering. • With Sm substitution, significant improvement in properties was observed. • Increase in magnetization for electrically poled sample is evidence of ME coupling. • Electric polarization is generated by applying magnetic field.

IgM-mediated opsonization and cytotoxicity in the shark.

Science.gov (United States)

McKinney, E C; Flajnik, M F

1997-02-01

Two types of cytotoxic reactions have been observed using cells from the nurse shark: spontaneous cytotoxicity mediated by cells of the macrophage lineage and antibody-dependent killing carried out by a different effector cell population. Previous data showed that removal of phagocytic cells using iron particles abolished macrophage-mediated killing, but not antibody-dependent reactions. The current study used single cell assays and showed that the effector of antibody-driven reactions was the neutrophil. Surprisingly, the mechanism of killing was shown to be phagocytosis mediated by both 7S and 19S immunoglobulin M (IgM). Reactions proceeded with as little as 0.01 microg of purified 19S or 7S IgM and were complete within 4-6 h. In contrast, purified immunoglobulin did not adsorb to macrophages and had no effect on target cell binding or cytotoxicity. Pretreatment of cells with cytochalasin D abolished the phagocytic reaction, but not spontaneous cytotoxicity. These data show that antibody-mediated killing results from opsonization and phagocytosis; the mechanism of macrophage killing is currently unknown. In addition, these data show that the shark neutrophil, not the macrophage lineage, carries a receptor for Fc mu.

Retention capacity of samarium (III) in zircon for it possible use in retaining walls for confinement of nuclear residues; Capacidad de retencion de samario (III) en circon para su posible uso en barreras de contencion para confinamiento de residuos nucleares

Energy Technology Data Exchange (ETDEWEB)

Garcia G, N

2006-07-01

Mexico, as country that produces part of its electric power by nuclear means, should put special emphasis in the development of technologies guided to the sure and long term confinement of the high level nuclear residuals. This work studies the capacity that has the natural zircon to retain to the samarium (III) in solution, by what due, firstly, to characterize the zircon for technical instrumental to determine the purity and characteristic of the mineral in study. The instrumental techniques that were used to carry out the physicochemical characterization were the neutron activation analysis (NAA), the infrared spectroscopy (IS), the thermal gravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), semiquantitative analysis, dispersive energy spectroscopy (EDS), X-ray diffraction (XRD) and luminescence technique. The characterization of the surface properties carries out by means of the determination of the surface area using the BET multipoint technique, acidity constants, hydration time, the determination of the point of null charge (pH{sub PCN}) and density of surface sites (D{sub s}). The luminescence techniques were useful to determine the optimal point hydration of the zircon and for the quantification of the samarium, for that here intends the development of both analysis techniques. With the adjustment of the titration curves in the FITEQL 4 package the constants of surface acidity in the solid/liquid interface were determined. To the finish of this study it was corroborated that the zircon is a mineral that presents appropriate characteristics to be proposed as a contention barrier for the deep geologic confinement. With regard to the study of adsorption that one carries out the samarium retention it is superior to 90% under the described conditions. This investigation could also be applicable in the confinement of dangerous industrial residuals. (Author)

Metal oxide nanoparticle mediated enhanced Raman scattering and its use in direct monitoring of interfacial chemical reactions.

Science.gov (United States)

Li, Li; Hutter, Tanya; Finnemore, Alexander S; Huang, Fu Min; Baumberg, Jeremy J; Elliott, Stephen R; Steiner, Ullrich; Mahajan, Sumeet

2012-08-08

Metal oxide nanoparticles (MONPs) have widespread usage across many disciplines, but monitoring molecular processes at their surfaces in situ has not been possible. Here we demonstrate that MONPs give highly enhanced (×10(4)) Raman scattering signals from molecules at the interface permitting direct monitoring of their reactions, when placed on top of flat metallic surfaces. Experiments with different metal oxide materials and molecules indicate that the enhancement is generic and operates at the single nanoparticle level. Simulations confirm that the amplification is principally electromagnetic and is a result of optical modulation of the underlying plasmonic metallic surface by MONPs, which act as scattering antennae and couple light into the confined region sandwiched by the underlying surface. Because of additional functionalities of metal oxides as magnetic, photoelectrochemical and catalytic materials, enhanced Raman scattering mediated by MONPs opens up significant opportunities in fundamental science, allowing direct tracking and understanding of application-specific transformations at such interfaces. We show a first example by monitoring the MONP-assisted photocatalytic decomposition reaction of an organic dye by individual nanoparticles.

The mechanism of the modified Ullmann reaction

NARCIS (Netherlands)

Sperotto, Elena; Klink, Gerard P.M. van; Koten, Gerard van; Vries, Johannes G. de

2010-01-01

The copper-mediated aromatic nucleophilic substitution reactions developed by Fritz Ullmann and Irma Goldberg required stoichiometric amounts of copper and very high reaction temperatures. Recently, it was found that addition of relatively cheap ligands (diamines, aminoalcohols, diketones, diols)

Effects of increasing doses of samarium-153-ethylenediaminetetramethylene phosphonate on axial and appendicular skeletal growth in juvenile rabbits

International Nuclear Information System (INIS)

Essman, Stephanie C.; Lewis, Michael R.; Fox, Derek B.

2008-01-01

Introduction: Targeted radiotherapy using samarium-153-ethylenediaminetetramethylene phosphonate ( 153 Sm-EDTMP) is currently under investigation for treatment of osteosarcoma. Osteosarcoma often occurs in children, and previous studies on a juvenile rabbit model demonstrated that clinically significant damage to developing physeal cartilage may occur as a result of systemic 153 Sm-EDTMP therapy. The aim of this study was to evaluate the late effects of 153 Sm-EDTMP on skeletal structures during growth to maturity and to determine if there is a dose response of 153 Sm-EDTMP on growth of long bones. Methods: Female 8-week-old New Zealand white rabbits were divided into three treatment groups plus controls. Each rabbit was intravenously administered a predetermined dose of 153 Sm-EDTMP. Multiple bones of each rabbit were radiographed every 2 months until physeal closure, with subsequent measurements made to assess for abbreviated bone growth. Statistical analyses were performed to determine the differences in bone length between groups, with significance set at P 153 Sm-EDTMP. Further investigation regarding the effects of bone-seeking radiopharmaceuticals on bone growth and physeal cartilage is warranted

Induction of Hypozincemia and Hepatic Metallothionein Synthesis in Hypersensitivity Reactions.

Science.gov (United States)

1978-06-19

cells to produce endogenous pyrogen (EP), the mediator of febrile response. Controversial evidence exists, however , concerning the differentiation of LEM...hypersensitivity reactions, Kampschmid t and Pulliam (1) proposed that leukocytic endogenous mediator (LEN) is released from phagocytic cells after... endogenous mediator(s) such as LEN, no conclusive evidence is available to indicate a mRNA requirement for the production of potential mediator(s

A copper-mediated reverse aromatic Finkelstein reaction in ionic liquid

Directory of Open Access Journals (Sweden)

Anh T.H. Nguyen

2018-03-01

Full Text Available We have developed a general method for reverse aromatic Finkelstein reactions. Good reaction yields were obtained when aryl iodides or aryl bromides were treated with copper halide salts as promoters in a 1-butyl-3-methylimidazolium bromide ([BMIM]Br ionic liquid (IL solvent at 140 °C for 8 h. Preliminary investigation supported that the copper salts were also the halide sources in halogen exchange reactions. The optimized conditions are applicable to a variety of substrates and have excellent functional group tolerance. Additionally, the [BMIM]Br solvent showed good stability for at least 10 consecutive runs. Results indicated that the [BMIM]Br solvent was recyclable for reverse aromatic Finkelstein reactions.

Micro-coulometric study of bioelectrochemical reaction coupled with TCA cycle.

Science.gov (United States)

Tsujimura, Seiya; Fukuda, Jun; Shirai, Osamu; Kano, Kenji; Sakai, Hideki; Tokita, Yuichi; Hatazawa, Tsuyonobu

2012-04-15

The mediated electro-enzymatic electrolysis systems based on the tricarboxylic acid (TCA) cycle reaction were examined on a micro-bulk electrolytic system. A series of the enzyme-catalyzed reactions in the TCA cycle was coupled with electrode reaction. Electrochemical oxidation of NADH was catalyzed by diaphorase with an aid of a redox mediator with a formal potential of -0.15 V vs. Ag|AgCl. The mediator was also able to shuttle electrons between succinate dehydrogenase and electrode. The charge during the electrolysis increased on each addition of dehydrogenase reaction in a cascade of the TCA cycle. However, the electrolysis efficiencies were close to or less than 90% because of the product inhibition. Lactate oxidation to acetyl-CoA catalyzed by two NAD-dependent dehydrogenases was coupled with the bioelectrochemical TCA cycle reaction to achieve the 12-electron oxidation of lactate to CO(2). The charge passed in the bioelectrocatalytic oxidation of 5 nmol of lactate was 4 mC, which corresponds to 70% of the electrolysis efficiency. Copyright © 2012 Elsevier B.V. All rights reserved.

An Adaptor Domain-Mediated Auto-Catalytic Interfacial Kinase Reaction

Science.gov (United States)

Liao, Xiaoli; Su, Jing; Mrksich, Milan

2010-01-01

This paper describes a model system for studying the auto-catalytic phosphorylation of an immobilized substrate by a kinase enzyme. This work uses self-assembled monolayers (SAMs) of alkanethiolates on gold to present the peptide substrate on a planar surface. Treatment of the monolayer with Abl kinase results in phosphorylation of the substrate. The phosphorylated peptide then serves as a ligand for the SH2 adaptor domain of the kinase and thereby directs the kinase activity to nearby peptide substrates. This directed reaction is intramolecular and proceeds with a faster rate than does the initial, intermolecular reaction, making this an auto-catalytic process. The kinetic non-linearity gives rise to properties that have no counterpart in the corresponding homogeneous phase reaction: in one example, the rate for phosphorylation of a mixture of two peptides is faster than the sum of the rates for phosphorylation of each peptide when presented alone. This work highlights the use of an adaptor domain in modulating the activity of a kinase enzyme for an immobilized substrate and offers a new approach for studying biochemical reactions in spatially inhomogeneous settings. PMID:19821459

Leprosy type 1 reactions and erythema nodosum leprosum

OpenAIRE

Kahawita,Indira P.; Walker,Stephen L.; Lockwood,Diana N.J.

2008-01-01

Leprosy reactions are a major cause of nerve damage and morbidity in a significant proportion of leprosy patients. Reactions are immunologically mediated and can occur even after successful completion of multi-drug therapy. This review focuses on the epidemiology, pathology and treatment of leprosy type 1 reactions, erythema nodosum leprosum and silent neuropathy.

Observation of near infrared and enhanced visible emissions from electroluminescent devices with organo samarium(III) complex

Energy Technology Data Exchange (ETDEWEB)

Chu, B [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, 16-Dong NanHu Road, Economic Development Area, Changchun, 130033 (China); Li, W L [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, 16-Dong NanHu Road, Economic Development Area, Changchun, 130033 (China); Hong, Z R [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, 16-Dong NanHu Road, Economic Development Area, Changchun, 130033 (China); Zang, F X [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, 16-Dong NanHu Road, Economic Development Area, Changchun, 130033 (China); Wei, H Z [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, 16-Dong NanHu Road, Economic Development Area, Changchun, 130033 (China); Wang, D Y [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, 16-Dong NanHu Road, Economic Development Area, Changchun, 130033 (China); Li, M T [Key Laboratory of the Excited States Process, Changchun Institute of Optics, Fine Mechanics and Physics, Chinese Academy of Sciences, 16-Dong NanHu Road, Economic Development Area, Changchun, 130033 (China); Lee, C S [Department of Physics and Materials Science, City University of Hong Kong, Hong Kong (China); Lee, S T [Department of Physics and Materials Science, City University of Hong Kong, Hong Kong (China)

2006-11-07

Samarium (dibenzoylmethanato){sub 3} bathophenanthroline (Sm(DBM){sub 3} bath) was employed as an emitting and electron transport layer in organic light emitting diodes (OLEDs), and narrow electroluminescent (EL) emissions of a Sm{sup 3+} ion were observed in the visible and near infrared (NIR) region, differing from those of the same devices with Eu{sup 3+}- or Tb{sup 3+}-complex EL devices with the same structure. The EL emissions of the Sm{sup 3+}-devices originate from transitions from {sup 4}G{sub 5/2} to the lower respective levels of Sm{sup 3+} ions. A maximum luminance of 490 cd m{sup -2} at 15 V and an EL efficiency of 0.6% at 0.17 mA cm{sup -2} were obtained in the visible region, and the improved efficiency should be attributed to introducing a transitional layer between the N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'-diphenyl-4,4'-diamine (TPD) film and the Sm(DBM){sub 3} bath film and the avoidance of interfacial exciplex emission in devices. Sharp emissions of Sm{sup 3+} ions in the NIR region were also observed under a lower threshold value less than 4.5 V.

Synthesis and characterization of samarium-doped ZnS nanoparticles: A novel visible light responsive photocatalyst

Energy Technology Data Exchange (ETDEWEB)

Hanifehpour, Younes, E-mail: y_hanifehpour@yu.ac.kr [School of Mechanical Engineering, Yeungnam University, Gyeongsan 712-749 (Korea, Republic of); Soltani, Behzad; Amani-Ghadim, Ali Reza; Hedayati, Behnam [Department of Chemistry, Faculty of Basic Sciences, Azarbaijan Shahid Madani University, Tabriz (Iran, Islamic Republic of); Khomami, Bamin [Department of Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN 37996 (United States); Joo, Sang Woo, E-mail: swjoo1@gmail.com [School of Mechanical Engineering, Yeungnam University, Gyeongsan 712-749 (Korea, Republic of)

2016-04-15

Highlights: • Sm-doped ZnS Nanomaterials were synthesized by hydrothermal method. • The as-prepared compounds were characterized by XRD, TEM, XPS, SEM and UV techniques. • The photocatalytic effect of compounds was determined by Reactive Red 43 degradation. • The degradation of RRed 43 followed the Langmuir–Hinshelwood kinetic model. - Abstract: We prepared pure and samarium-doped ZnS (Sm{sub x}Zn{sub 1−x}S{sub 1+0.5x}) nanoparticles via hydrothermal process at 160 °C for 24 h. XRD analysis shows that the particles were well crystallized and corresponds to a cubic sphalerite phase. SEM and TEM images indicate that the sizes of the particles were in the range of 20–60 nm. The photocatalytic activity of Sm-doped ZnS nanoparticles was evaluated by monitoring the decolorization of Reactive Red 43 in aqueous solution under visible light irradiation. The color removal efficiency of Sm{sub 0.04}Zn{sub 0.96}S and pure ZnS was 95.1% and 28.7% after 120 min of treatment, respectively. Among the different amounts of dopant agent used, 4% Sm-doped ZnS nanoparticles indicated the highest decolorization. We found that the presence of inorganic ions such as Cl{sup −}, CO{sub 3}{sup 2−} and other radical scavengers such as buthanol and isopropyl alcohol reduced the decolorization efficiency.

A systematic review: can one prescribe carbapenems to patients with IgE-mediated allergy to penicillins or cephalosporins?

Science.gov (United States)

Kula, Brittany; Djordjevic, Gordana; Robinson, Joan L

2014-10-15

Cross-reactivity between penicillins or cephalosporins and carbapenems is anticipated as all have a beta lactam ring. However, the true incidence of immunoglobulin (Ig)E-mediated cross-reactivity is not known. A systematic review was conducted to collect and combine all published data on children and adults reported to have a clinical history of IgE-mediated hypersensitivity to a penicillin and/or cephalosporin who were subsequently given a carbapenem. Reactions were classified as proven, suspected, or possible IgE-mediated and non-IgE-mediated. Ten studies and 12 case reports describing 854 participants fit the study criteria. For patients with previous proven, suspected, or possible IgE-mediated penicillin reactions (N = 838), the incidence of any type of suspected hypersensitivity reaction to a carbapenem was 36/838 (4.3%; 95% confidence interval [CI], 3.1%-5.9%) and the incidence of proven (1/838), suspected (0/838), or possible (19/838) IgE-mediated reactions was 20/838 (2.4%; 95% CI, 1.6%-3.7%). Of the subset of patients with positive penicillin skin tests (n = 295), only 1 had a hypersensitivity reaction (0.3%; 95% CI, .06%-1.9%), and this was a possible IgE-mediated reaction. For patients with previous proven, suspected, or possible IgE-mediated cephalosporin reactions (N = 12), the incidence of any type of hypersensitivity reaction to a carbapenem was 3/12 (25%); this included 2 non-IgE-mediated reactions and 1 possible IgE-mediated reaction. The cross-reactivity between penicillins and carbapenems for IgE-mediated reactions is very low, but caution is still advised. Cross-reactivity rates may be higher between cephalosporins and carbapenems; however, minimal data are available. © The Author 2014. Published by Oxford University Press on behalf of the Infectious Diseases Society of America. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Solvent-free microwave-mediated Michael addition reactions

Indian Academy of Sciences (India)

Unknown

obviously difficult to scale up. In this context ... eco-friendly features such as, (i) no solvent is required to conduct the ... water soluble, addition of reaction mixture after com- ..... Yield: 855 mg (89%; viscous liquid). 3.4 Ethyl .... Jung M E 1993 Comprehensive organic synthesis ... Leshcheva I F and Bundel Y G 1997 Mendeleev.

OXIDATIVE DEHYDROGENATION OF PROPANE BY RARE EARTH PHOSPHATES SUPPORTED ON AL-PILC

Directory of Open Access Journals (Sweden)

Carolina De Los Santos

2012-12-01

Full Text Available Catalytic activity in propane oxidative dehydrogenation of rare earth phosphates LnPO4 (where Ln = La, Ce, Pr, Nd, Sm and of the same supported by an aluminum pillared clay, of high specific surface area, is presented. The solids were characterized by TGA, XRD, nitrogen adsorption and immediate analysis after reaction in order to determine eventual carbon formation. Catalytic assays were performed at temperatures in the range 400oC-600oC, the reaction mixture was C3H8/O2/Ar = 10/10/80. All the catalysts were active. The reaction products were H2, CO, CO2, CH4, C2H4 and C3H6 and there were no organic oxygenated compounds detected. Although all the investigated systems were active, the Al-PILC supported catalysts presented a higher activity than the bulk materials. In this context, the samarium supported catalyst showed a propene yield increase from 4% to 10% compared with bulk samarium phosphate at 600°C. This effect was attributed to the increase in the specific surface area.

Study for the determination of samarium, europium,terbium, dysprosium and yttrium in gadolinium oxide matrix by means of atomic absorption spectrophotometry using a graphite furnace

International Nuclear Information System (INIS)

Caires, A.C.F.

1985-01-01

A study for determination of samarium, europium, terbium, dysprosium and yttrium in a gadolinium oxide matrix by atomic absorption spectrophotometry using a graphite furnace is presented. The best charrring and atomization conditions were estabilished for each element, the most convenient ressonance lines being selected as well. The study was carried out for the mentioned lanthanides both when pure and when in binary mixtures with gadolinium, besides those where all for them were together with gadolinium. The determination limits for pure lanthanides were found to be between 1.3 and 9.6 ng assuming a 20% relative standard deviation as acceptable. The detection limits were in the range 0.51 and 7.5 ng, assuming as positive any answer higher than twofold the standard deviation. (author) [pt

Detection of DNA damage based on metal-mediated molecular beacon and DNA strands displacement reaction

Science.gov (United States)

Xiong, Yanxiang; Wei, Min; Wei, Wei; Yin, Lihong; Pu, Yuepu; Liu, Songqin

2014-01-01

DNA hairpin structure probes are usually designed by forming intra-molecular duplex based on Watson-Crick hydrogen bonds. In this paper, a molecular beacon based on silver ions-mediated cytosine-Ag+-cytosine base pairs was used to detect DNA. The inherent characteristic of the metal ligation facilitated the design of functional probe and the adjustment of its binding strength compared to traditional DNA hairpin structure probes, which make it be used to detect DNA in a simple, rapid and easy way with the help of DNA strands displacement reaction. The method was sensitive and also possesses the good specificity to differentiate the single base mismatched DNA from the complementary DNA. It was also successfully applied to study the damage effect of classic genotoxicity chemicals such as styrene oxide and sodium arsenite on DNA, which was significant in food science, environmental science and pharmaceutical science.

Anchoring samarium oxide nanoparticles on reduced graphene oxide for high-performance supercapacitor

Energy Technology Data Exchange (ETDEWEB)

Dezfuli, Amin Shiralizadeh [Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran (Iran, Islamic Republic of); Ganjali, Mohammad Reza, E-mail: ganjali@khayam.ut.ac.ir [Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran (Iran, Islamic Republic of); Biosensor Research Center, Endocrinology & Metabolism Molecular-Cellular Sciences Institute, Tehran University of Medical Sciences, Tehran (Iran, Islamic Republic of); Naderi, Hamid Reza [Center of Excellence in Electrochemistry, Faculty of Chemistry, University of Tehran, Tehran (Iran, Islamic Republic of)

2017-04-30

Highlights: • Samarium oxide nanoparticles have been anchored on the surface of reduced graphene oxide for the first time. • Sm{sub 2}O{sub 3}/RGO nanocomposite show high capacitance, good rate and cycling performance. • Sm{sub 2}O{sub 3}/RGO nanocomposite can serve as efficient electrode material for energy storage. • The best composite electrode exhibits specific capacitance of 321 F g{sup −1} in 2 mV s{sup −1}. - Abstract: We have synthesized Sm{sub 2}O{sub 3} nanoparticles (SmNs) and anchored them onto the surface of reduced graphene oxide (RGO) through a self-assembly thereof by utilizing a facile sonochemical procedure. The nanomaterials were characterized by means of powder X-ray diffraction (XRD), Field-emission scanning electron microscopy (FE-SEM), fourier transform infrared spectroscopy (FT-IR) spectra, and X-ray photoelectron spectroscopy (XPS). As the next step, the supercapacitive behavior of the resulting nanocomposites were investigated when used as electrode material, through with cyclic voltammetric (CV), galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) techniques. The SmNs decorated RGO (SmN-RGO) nanocomposites were found to possess a specific capacitance (SC) of 321 F g{sup −1} when used in a 0.5 M Na{sub 2}SO{sub 4} solution as an electrolyte, in a scan rate of 2 mV s{sup −1}. The SC of the SmN-RGO based electrodes were also found to be 268 F g{sup −1} at a current density of 2 A g{sup −1} through galvanostatic charge-discharge tests. The outstanding properties of the SmN-RGOs were attributed to synergy of the high charge mobility of SmNs and the flexibility of the sheets of RGOs. Additionally, the nano-composite revealed a unique cycling durability (maintaining 99% of its SC even after 4000 cycles).

Toehold-mediated strand displacement reaction-dependent fluorescent strategy for sensitive detection of uracil-DNA glycosylase activity.

Science.gov (United States)

Wu, Yushu; Wang, Lei; Jiang, Wei

2017-03-15

Sensitive detection of uracil-DNA glycosylase (UDG) activity is beneficial for evaluating the repairing process of DNA lesions. Here, toehold-mediated strand displacement reaction (TSDR)-dependent fluorescent strategy was constructed for sensitive detection of UDG activity. A single-stranded DNA (ssDNA) probe with two uracil bases and a trigger sequence were designed. A hairpin probe with toehold domain was designed, and a reporter probe was also designed. Under the action of UDG, two uracil bases were removed from ssDNA probe, generating apurinic/apyrimidinic (AP) sites. Then, the AP sites could inhibit the TSDR between ssDNA probe and hairpin probe, leaving the trigger sequence in ssDNA probe still free. Subsequently, the trigger sequence was annealed with the reporter probe, initiating the polymerization and nicking amplification reaction. As a result, numerous G-quadruplex (G4) structures were formed, which could bind with N-methyl-mesoporphyrin IX (NMM) to generate enhanced fluorescent signal. In the absence of UDG, the ssDNA probe could hybridize with the toehold domain of the hairpin probe to initiate TSDR, blocking the trigger sequence, and then the subsequent amplification reaction would not occur. The proposed strategy was successfully implemented for detecting UDG activity with a detection limit of 2.7×10 -5 U/mL. Moreover, the strategy could distinguish UDG well from other interference enzymes. Furthermore, the strategy was also applied for detecting UDG activity in HeLa cells lysate with low effect of cellular components. These results indicated that the proposed strategy offered a promising tool for sensitive quantification of UDG activity in UDG-related function study and disease prognosis. Copyright © 2016 Elsevier B.V. All rights reserved.

Mechanisms in adverse reactions to food. The ear

DEFF Research Database (Denmark)

Høst, A

1995-01-01

Otitis media with effusion is rarely caused by allergy to food. Allergic inflammation in the nasal mucosa, mainly due to IgE-mediated reactions to foods, may cause eustachian tube dysfunction and subsequent otitis media with effusion. Inflammatory mediators from the nasal mucosa transported via...

Reaction limited aggregation in surfactant-mediated epitaxy

Science.gov (United States)

Wu, Jing; Liu, Bang-Gui; Zhang, Zhenyu; Wang, E. G.

2000-05-01

A theoretical model for reaction limited aggregation (RLA) is introduced to study the effect of a monolayer of surfactant on the formation of two-dimensional islands in heteroepitaxial and homoepitaxial growth. In this model the basic atomic processes are considered as follows. A stable island consists of the adatoms that have exchanged positions with the surfactant atoms beneath them. Movable active adatoms may (a) diffuse on the surfactant terrace, (b) exchange positions with the surfactant atoms beneath them and become island seeds (seed exchange), or (c) stick to stable islands and become stuck but still active adatoms. The rate-limiting step for the formation of a stable island is the seed exchange. Furthermore, a stuck but still active adatom must overcome a sizable potential-energy barrier to exchange positions with the surfactant atom beneath it and become a member of the stable island (aided exchange). The seed exchange process can occur with an adatom or collectively with an addimer. In the case of dimer exchange, the diffusing adatoms on the surfactant terrace can meet and (after exchanging) form stable dimers, which can then become island seeds. Systematic kinetic Monte Carlo simulations and rate-equation analysis of the model are carried out. The key finding of these simulations is that a counterintuitive fractal-to-compact island shape transition can be induced either by increasing deposition flux or by decreasing growth temperature. This major qualitative conclusion is valid for both the monomer and the dimer seed exchanges and for two different substrate lattices (square and triangular, respectively), although there are some quantitative differences in the flux and temperature dependence of the island density. The shape transition observed is contrary to the prediction of the classic diffusion-limited aggregation (DLA) theory, but in excellent qualitative agreement with recent experiments. In rationalizing the main finding, it is crucial to realize

Anger and health in dementia caregivers: exploring the mediation effect of optimism.

Science.gov (United States)

López, J; Romero-Moreno, R; Márquez-González, M; Losada, A

2015-04-01

Although previous studies indicate a negative association between caregivers' anger and health, the potential mechanisms linking this relationship are not yet fully understood. The aim of this study was to explore the potential mediating role of optimism in the relationship between anger and caregivers' physical health. Dementia caregivers (n = 108) were interviewed and filled out instruments assessing their anger (reaction), optimism and health (vitality). A mediational model was tested to determine whether optimism partially mediated the relationship between anger and vitality. Angry reaction was negatively associated with optimism and vitality; optimism was positively associated with vitality. Finally, the relationship between angry reaction and vitality decreased when optimism was entered simultaneously. A non-parametric bootstrap approach confirmed that optimism significantly mediated some of the relationship between angry reaction and vitality. These findings suggest that low optimism may help explain the association between caregivers' anger and reduced sense of vitality. The results provide a specific target for intervention with caregivers. Copyright © 2013 John Wiley & Sons, Ltd.

Biologically mediated dissolution of volcanic glass in seawater

NARCIS (Netherlands)

Staudigel, H; Yayanos, A; Chastain, R; Davies, G.T.; Verdurmen, E.A Th; Schiffmann, P; Bourcier, R; de Baar, H.J.W.

1998-01-01

We studied the effects of biological mediation on the dissolution of basaltic glass in seawater. Experiments with typical seawater microbial populations were contrasted with a sterile control, and reactions were monitored chemically and isotopically. Biologically mediated experiments produce twice

A convenient method for the conversion of N-acyloxazolidinones to hydroxamic acids.

Science.gov (United States)

Sibi, Mukund P; Hasegawa, Hikaru; Ghorpade, Sandeep R

2002-10-03

Treatment of N-acyloxazolidinones with hydroxylamines using samarium triflate as a Lewis acid provides the corresponding hydroxamic acids in 50-98% yields at room temperature. The conversion proceeds with high degree of chemoselectivity and without racemization of chiral centers alpha- to the acyl group. [reaction: see text

Samarium-modified vanadium phosphate catalyst for the selective oxidation of n-butane to maleic anhydride

International Nuclear Information System (INIS)

Wu, Hua-Yi; Wang, Hai-Bo; Liu, Xin-Hua; Li, Jian-Hui; Yang, Mei-Hua; Huang, Chuan-Jing; Weng, Wei-Zheng; Wan, Hui-Lin

2015-01-01

Graphical abstract: The addition of a small amount of Sm into VPO catalyst brought about great changes in its physicochemical properties such as surface area, surface morphology, phase composition and redox property, thus leading to a higher catalytic performance in the selective oxidation of n-butane to maleic anhydride, as compared to the undoped VPO catalyst. - Highlights: • The addition of Sm leads to great changes in the structure of VPO catalyst. • Sm improves performance of VPO for oxidation of n-butane to maleic anhydride. • Catalytic performance is closely related to structure of VPO catalyst. - Abstract: A series of samarium-modified vanadium phosphate catalysts were prepared and studied in selective oxidation of n-butane to maleic anhydride. The catalytic evaluation showed that Sm modification significantly increased the overall n-butane conversion and intrinsic activity. N 2 -adsorption, XRD, SEM, Raman, XPS, EPR and H 2 -TPR techniques were used to investigate the intrinsic difference among these catalysts. The results revealed that the addition of Sm to VPO catalyst can increase the surface area of the catalyst, lead to a significant change in catalyst morphology from plate-like structure into rosette-shape clusters, and largely promote the formation of (VO) 2 P 2 O 7 . All of these were related to the different catalytic performance of Sm-doped and undoped VPO catalysts. The roles of the different VOPO 4 phases and the influence of Sm were also described and discussed

The Role of Psychological Stress Reactions in the Longitudinal Relation Between Workplace Bullying and Turnover.

Science.gov (United States)

Nabe-Nielsen, Kirsten; Grynderup, Matias Brødsgaard; Conway, Paul Maurice; Clausen, Thomas; Bonde, Jens Peter; Garde, Anne Helene; Hogh, Annie; Kaerlev, Linda; Török, Eszter; Hansen, Åse Marie

2017-07-01

To investigate the association between workplace bullying and change of job/unemployment, and to investigate whether psychological stress reactions constitute a potential pathway linking workplace bullying and change of job/unemployment. We used questionnaire data on workplace bullying and psychological stress reactions and register data on change of job/unemployment. We applied a multiple pathway approach to estimate the proportion of the association between workplace bullying and subsequent change of job/unemployment that was potentially mediated by psychological stress reactions. Workplace bullying was associated with risk of change of job (odds ratio [OR] = 1.35; 95% confidence interval [CI]: 1.06-1.72; 24% potentially mediated by psychological stress reactions) and unemployment (OR = 4.90; 95% CI: 3.18-7.55; 19% potentially mediated by psychological stress reactions). Workplace bullying has important consequences for labor market outcomes. Psychological stress reactions may play a vital role in this process.

Reconstitution of DNA strand exchange mediated by Rhp51 recombinase and two mediators.

Directory of Open Access Journals (Sweden)

Yumiko Kurokawa

2008-04-01

Full Text Available In the fission yeast Schizosaccharomyces pombe, genetic evidence suggests that two mediators, Rad22 (the S. pombe Rad52 homolog and the Swi5-Sfr1 complex, participate in a common pathway of Rhp51 (the S. pombe Rad51 homolog-mediated homologous recombination (HR and HR repair. Here, we have demonstrated an in vitro reconstitution of the central step of DNA strand exchange during HR. Our system consists entirely of homogeneously purified proteins, including Rhp51, the two mediators, and replication protein A (RPA, which reflects genetic requirements in vivo. Using this system, we present the first robust biochemical evidence that concerted action of the two mediators directs the loading of Rhp51 onto single-stranded DNA (ssDNA precoated with RPA. Dissection of the reaction reveals that Rad22 overcomes the inhibitory effect of RPA on Rhp51-Swi5-Sfr1-mediated strand exchange. In addition, Rad22 negates the requirement for a strict order of protein addition to the in vitro system. However, despite the presence of Rad22, Swi5-Sfr1 is still essential for strand exchange. Importantly, Rhp51, but neither Rad22 nor the Swi5-Sfr1 mediator, is the factor that displaces RPA from ssDNA. Swi5-Sfr1 stabilizes Rhp51-ssDNA filaments in an ATP-dependent manner, and this stabilization is correlated with activation of Rhp51 for the strand exchange reaction. Rad22 alone cannot activate the Rhp51 presynaptic filament. AMP-PNP, a nonhydrolyzable ATP analog, induces a similar stabilization of Rhp51, but this stabilization is independent of Swi5-Sfr1. However, hydrolysis of ATP is required for processive strand transfer, which results in the formation of a long heteroduplex. Our in vitro reconstitution system has revealed that the two mediators have indispensable, but distinct, roles for mediating Rhp51 loading onto RPA-precoated ssDNA.

Dgroup: DG01196 [KEGG MEDICUS

Lifescience Database Archive (English)

Full Text Available DG01196 Chemical ... DGroup Samarium (153Sm) lexidronam ... D08504 ... Samarium (153Sm) lexidron...am (INN) D05795 ... Samarium Sm 153 lexidronam pentasodium (USAN); Samarium (153Sm) lexidronam sodium (JA

Loop-mediated isothermal amplification (LAMP) based detection of ...

African Journals Online (AJOL)

SAM

2014-05-07

May 7, 2014 ... 2 months for growing in a culture. Therefore, to control .... The LAMP reaction is carried out in a 25 µL reaction mixture containing ..... J. Fish Dis. 32(6):491-497. Goto M, Honda E, Ogura A, Nomoto A, Hanaki K (2009). Colorimetric detection of loop-mediated isothermal amplification reaction by using hydroxy ...

Methanol Adsorption and Reaction on Samaria Thin Films on Pt(111

Directory of Open Access Journals (Sweden)

Jin-Hao Jhang

2015-09-01

Full Text Available We investigated the adsorption and reaction of methanol on continuous and discontinuous films of samarium oxide (SmOx grown on Pt(111 in ultrahigh vacuum. The methanol decomposition was studied by temperature programmed desorption (TPD and infrared reflection absorption spectroscopy (IRRAS, while structural changes of the oxide surface were monitored by low-energy electron diffraction (LEED. Methanol dehydrogenates to adsorbed methoxy species on both the continuous and discontinuous SmOx films, eventually leading to the desorption of CO and H2 which desorbs at temperatures in the range 400–600 K. Small quantities of CO2 are also detected mainly on as-prepared Sm2O3 thin films, but the production of CO2 is limited during repeated TPD runs. The discontinuous film exhibits the highest reactivity compared to the continuous film and the Pt(111 substrate. The reactivity of methanol on reduced and reoxidized films was also investigated, revealing how SmOx structures influence the chemical behavior. Over repeated TPD experiments, a SmOx structural/chemical equilibrium condition is found which can be approached either from oxidized or reduced films. We also observed hydrogen absence in TPD which indicates that hydrogen is stored either in SmOx films or as OH groups on the SmOx surfaces.

Bis(phenolate)amine-supported lanthanide borohydride complexes for styrene and trans-1,4-isoprene (co-)polymerisations

NARCIS (Netherlands)

Bonnet, Fanny; Dyer, Hellen E.; El Kinani, Yassine; Dietz, Carin; Roussel, Pascal; Bria, Marc; Visseaux, Marc; Zinck, Philippe; Mountford, Philip

2015-01-01

New bis(phenolate)amine-supported neodymium borohydride complexes and their previously reported samarium analogues were tested as catalysts for the polymerisation of styrene and isoprene. Reaction of Na2O2NL (L = py, OMe, NMe2) with Nd(BH4)3(THF)3 afforded the borohydride complexes

An experiment using neutron activation analysis and a rare earth element to mark cotton plants and two insects that feed on them

Energy Technology Data Exchange (ETDEWEB)

Showler, Allan T. [USDA-ARS IFNRRU, Kika de la Garza Subtropical Agricultural Research Center, 2413 East Highway 83, Weslaco, TX 78596 (United States)]. E-mail: ashowler@weslaco.ars.usda.gov; James, William D. [Elemental Analysis Laboratory, 3144 Texas A and M University, College Station, TX 77843-3144 (United States); Armstrong, John S. [USDA-ARS BIRU, Kika de la Garza Subtropical Agricultural Research Center, 2413 East Highway 83, Weslaco, TX 78596 (United States); Westbrook, John K. [USDA-ARS APMRU, 2771 F and B Road, College Station, TX 77845-4966 (United States)

2006-08-15

Studies on insect dispersal and other behaviors can benefit from using markers that will not alter flight and fitness. Rare earth elements, such as samarium (Sm), have been used as ingested markers of some insects and detected using neutron activation analysis (NAA). In this study, samarium nitrate hexahydrate was mixed into artificial diet for boll weevils, Anthonomus grandis grandis Boheman (Coleoptera: Curculionidae), at different dosages and in water used to irrigate cotton, Gossypium hirsutum L. Samarium was detected in adult boll weevils fed on the samarium-labeled diet, but not after 5 or 10 days of being switched to non-labeled diet, even if the insects were given labeled diet for as long as 7 consecutive days. Introduced in irrigation water, 1% samarium (m/m) was detectable in cotton squares and leaf tissue. However, boll weevil adults fed samarium-labeled squares did not retain detectable levels of samarium, nor did boll weevil adults reared to adulthood from samarium-labeled squares. Fourth instar beet armyworms, Spodoptera exigua (Huebner) (Noctuidae: Lepidoptera), fed on samarium-labeled cotton leaves obtained enough samarium for NAA detection, but adult moths reared from them did not have detectable amounts of samarium. Although samarium can be useful as a marker when insects are presented with a continuous pulse of the label, elements that are assimilated by the insect would be more useful if a continuous infusion of the marker cannot be provided.

Bimolecular reactions of carbenes: Proton transfer mechanism

Science.gov (United States)

Abu-Saleh, Abd Al-Aziz A.; Almatarneh, Mansour H.; Poirier, Raymond A.

2018-04-01

Here we report the bimolecular reaction of trifluoromethylhydroxycarbene conformers and the water-mediated mechanism of the 1,2-proton shift for the unimolecular trans-conformer by using quantum chemical calculations. The CCSD(T)/cc-pVTZ//MP2/cc-pVDZ potential-energy profile of the bimolecular reaction of cis- and trans-trifluoromethylhydroxycarbene, shows the lowest gas-phase barrier height of 13 kJ mol-1 compared to the recently reported value of 128 kJ mol-1 for the unimolecular reaction. We expect bimolecular reactions of carbene's stereoisomers will open a valuable field for new and useful synthetic strategies.

Automated chromatographic laccase-mediator-system activity assay.

Science.gov (United States)

Anders, Nico; Schelden, Maximilian; Roth, Simon; Spiess, Antje C

2017-08-01

To study the interaction of laccases, mediators, and substrates in laccase-mediator systems (LMS), an on-line measurement was developed using high performance anion exchange chromatography equipped with a CarboPac™ PA 100 column coupled to pulsed amperometric detection (HPAEC-PAD). The developed method was optimized for overall chromatographic run time (45 to 120 min) and automated sample drawing. As an example, the Trametes versicolor laccase induced oxidation of 1-(3,4-dimethoxyphenyl)-2-(2-methoxyphenoxy)-1,3-dihydroxypropane (adlerol) using 1-hydroxybenzotriazole (HBT) as mediator was measured and analyzed on-line. Since the Au electrode of the PAD detects only hydroxyl group containing substances with a limit of detection being in the milligram/liter range, not all products are measureable. Therefore, this method was applied for the quantification of adlerol, and-based on adlerol conversion-for the quantification of the LMS activity at a specific T. versicolor laccase/HBT ratio. The automated chromatographic activity assay allowed for a defined reaction start of all laccase-mediator-system reactions mixtures, and the LMS reaction progress was automatically monitored for 48 h. The automatization enabled an integrated monitoring overnight and over-weekend and minimized all manual errors such as pipetting of solutions accordingly. The activity of the LMS based on adlerol consumption was determined to 0.47 U/mg protein for a laccase/mediator ratio of 1.75 U laccase/g HBT. In the future, the automated method will allow for a fast screening of combinations of laccases, mediators, and substrates which are efficient for lignin modification. In particular, it allows for a fast and easy quantification of the oxidizing activity of an LMS on a lignin-related substrate which is not covered by typical colorimetric laccase assays. ᅟ.

Coulometric bioelectrocatalytic reactions based on NAD-dependent dehydrogenases in tricarboxylic acid cycle

Energy Technology Data Exchange (ETDEWEB)

Fukuda, Jun [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan); Tsujimura, Seiya [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)], E-mail: seiya@kais.kyoto-u.ac.jp; Kano, Kenji [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502 (Japan)], E-mail: kkano@kais.kyoto-u.ac.jp

2008-12-30

This paper describes the characterization of mediated electro-enzymatic electrolysis systems based on NAD-dependent dehydrogenase reactions in the tricarboxylic acid (TCA) cycle. A micro-bulk electrolysis system with a carbon felt anode immersed in an electrolysis solution with a value of about 10 {mu}L was constructed for coulometric analysis of the substrate oxidation. Diaphorase (DI) was used to couple the NAD-dependent dehydrogenase reaction with the anode reaction of a suitable redox mediator. We focused on three types of NAD-dependant dehydrogenases reactions in this research: (1) isocitrate oxidation, in which the standard Gibbs energy change ({delta}G{sup o}') is negative; (2) {alpha}-ketoglutarate oxidation, which involves an electrochemically active coenzyme A (CoA); and (3) malate oxidation, which is thermodynamically unfavorable because of a large positive {delta}G{sup o}' value. The complete electrolysis of isocitrate was easily achieved, supporting the effective re-oxidation of NADH in the diaphorase-catalyzed electrochemical reaction. CoA was unfavorably oxidized at the electrodes in the presence of some mediators. The electrocatalytic oxidation of CoA was suppressed and the quantitative electrochemical oxidation of {alpha}-ketoglutarate was achieved by selecting a suitable mediator with negligibly slow electron transfer kinetics with CoA. The uphill malate oxidation was susceptible to product inhibition in the bioelectrochemical system, although NADH generated in the malate dehydrogenase reaction was immediately oxidized in the electrochemical system. The inhibition was successfully suppressed by linking citrate synthase to quench oxaloacetate and to make the total {delta}G{sup o}' value negative.

Coulometric bioelectrocatalytic reactions based on NAD-dependent dehydrogenases in tricarboxylic acid cycle

International Nuclear Information System (INIS)

Fukuda, Jun; Tsujimura, Seiya; Kano, Kenji

2008-01-01

This paper describes the characterization of mediated electro-enzymatic electrolysis systems based on NAD-dependent dehydrogenase reactions in the tricarboxylic acid (TCA) cycle. A micro-bulk electrolysis system with a carbon felt anode immersed in an electrolysis solution with a value of about 10 μL was constructed for coulometric analysis of the substrate oxidation. Diaphorase (DI) was used to couple the NAD-dependent dehydrogenase reaction with the anode reaction of a suitable redox mediator. We focused on three types of NAD-dependant dehydrogenases reactions in this research: (1) isocitrate oxidation, in which the standard Gibbs energy change (ΔG o ') is negative; (2) α-ketoglutarate oxidation, which involves an electrochemically active coenzyme A (CoA); and (3) malate oxidation, which is thermodynamically unfavorable because of a large positive ΔG o ' value. The complete electrolysis of isocitrate was easily achieved, supporting the effective re-oxidation of NADH in the diaphorase-catalyzed electrochemical reaction. CoA was unfavorably oxidized at the electrodes in the presence of some mediators. The electrocatalytic oxidation of CoA was suppressed and the quantitative electrochemical oxidation of α-ketoglutarate was achieved by selecting a suitable mediator with negligibly slow electron transfer kinetics with CoA. The uphill malate oxidation was susceptible to product inhibition in the bioelectrochemical system, although NADH generated in the malate dehydrogenase reaction was immediately oxidized in the electrochemical system. The inhibition was successfully suppressed by linking citrate synthase to quench oxaloacetate and to make the total ΔG o ' value negative

Highly selective and sensitive detection of miRNA based on toehold-mediated strand displacement reaction and DNA tetrahedron substrate.

Science.gov (United States)

Li, Wei; Jiang, Wei; Ding, Yongshun; Wang, Lei

2015-09-15

MicroRNAs (miRNAs) play important roles in a variety of biological processes and have been regarded as tumor biomarkers in cancer diagnosis and prognosis. In this work, a single-molecule counting method for miRNA analysis was proposed based on toehold-mediated strand displacement reaction (SDR) and DNA tetrahedron substrate. Firstly, a specially designed DNA tetrahedron was assembled with a hairpin at one of the vertex, which has an overhanging toehold domain. Then, the DNA tetrahedron was immobilized on the epoxy-functional glass slide by epoxy-amine reaction, forming a DNA tetrahedron substrate. Next, the target miRNA perhybridized with the toehold domain and initiated a strand displacement reaction along with the unfolding of the hairpin, realizing the selective recognization of miRNA. Finally, a biotin labeled detection DNA was hybridized with the new emerging single strand and the streptavidin coated QDs were used as fluorescent probes. Fluorescent images were acquired via epi-fluorescence microscopy, the numbers of fluorescence dots were counted one by one for quantification. The detection limit is 5 fM, which displayed an excellent sensitivity. Moreover, the proposed method which can accurately be identified the target miRNA among its family members, demonstrated an admirable selectivity. Furthermore, miRNA analysis in total RNA samples from human lung tissues was performed, suggesting the feasibility of this method for quantitative detection of miRNA in biomedical research and early clinical diagnostics. Copyright © 2015 Elsevier B.V. All rights reserved.

Live-Cell MicroRNA Imaging through MnO2 Nanosheet-Mediated DD-A Hybridization Chain Reaction.

Science.gov (United States)

Ou, Min; Huang, Jin; Yang, Xiaohai; He, Xiaoxiao; Quan, Ke; Yang, Yanjing; Xie, Nuli; Li, Jing; Wang, Kemin

2018-01-18

Innovative techniques to visualize native microRNAs (miRNAs) in live cells can dramatically impact current research on the roles of miRNA in biology and medicine. Here, we report a novel approach for live-cell miRNA imaging using a biodegradable MnO 2 nanosheet-mediated DD-A FRET hybridization chain reaction (HCR). The MnO 2 nanosheets can adsorb DNA hairpin probes and deliver them into live cells. After entering cells, the MnO 2 nanosheets are degraded by cellular GSH. Then, the target miR-21 triggers cascaded assembly of the liberated hairpin probes into long dsDNA polymers, which brings each two FAMs (donor) and one TAMRA (acceptor) into close proximity to generate significantly enhanced DD-A FRET signals, which was discovered and proven by our previous report. We think the developed approach can serve as an excellent intracellular miRNAs detection tool, which promises the potential for biological and disease studies. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of 2-iodobenzamides and 3-(iodoacetamide)benzamides linked to D-galactose and their tri-n-butyltin hydride-mediated radical carbocyclization reactions

International Nuclear Information System (INIS)

Leal, Daniel Henriques Soares; Queiroga, Carla Graziella; Pires, Magno Carvalho; Prado, Maria Auxiliadra Fontes; Alves, Ricardo Jose; Cesar, Amary

2009-01-01

Starting from methyl 6-O-allyl-4-azido-2,3-di-O-benzyl-4-deoxy-a-D-galactopyranoside, four new derivatives containing 2-iodobenzamide and 3-(iodoacetamide)benzamido groups were synthesized. These four compounds were submitted to tri-n-butyltin hydride mediated radical cyclization reactions, resulting in two macrolactams from 11- and 15-endo aryl radical cyclization. The corresponding four hydrogenolysis products were also obtained. The structures of the new compounds were elucidated by 1 H and 13 C NMR spectroscopy, DEPT, COSY, HMQC and HMBC experiments. (author)

Fabrication and properties of samarium doped calcium sulphate thin films using spray pyrolysis technique

Energy Technology Data Exchange (ETDEWEB)

Reghima, Meriem [Université Tunis El Manar, Faculté des Sciences de Tunis, Département de Physique, LR99ES13 Laboratoire de Physique de la Matière Condensée (LPMC), 2092 Tunis, Tunisie (Tunisia); Institut d' Electronique et des systèmes, Unité Mixte de Recherche 5214 UM2-CNRS (ST2i) – Université Montpellier, 860 rue de Saint Priest, Bâtiment 5, 34097 Montpellier (France); Faculté des Sciences de Bizerte, Université de Carthage, Zarzouna 7021 (Tunisia); Guasch, Cathy [Institut d' Electronique et des systèmes, Unité Mixte de Recherche 5214 UM2-CNRS (ST2i) – Université Montpellier, 860 rue de Saint Priest, Bâtiment 5, 34097 Montpellier (France); Azzaza, Sonia; Alleg, Safia [Laboratoire de Magnétisme et Spectroscopie des Solides (LM2S), Département de Physique, Faculté des Sciences, Université Badji Mokhtar Annaba, B.P. 12, 23000 Annaba (Algeria); Kamoun-Turki, Najoua [Université Tunis El Manar, Faculté des Sciences de Tunis, Département de Physique, LR99ES13 Laboratoire de Physique de la Matière Condensée (LPMC), 2092 Tunis, Tunisie (Tunisia)

2016-10-01

Using low cost spray pyrolysis technique, polycrystalline CaSO{sub 4} thin films were successfully grown on a glass substrate with a thickness of about 1 μm. Samarium doping has been performed on CaSO{sub 4} thin films to explore luminescence properties. The characterizations of these films were carried out using X-ray diffraction, Scanning Electron Microscopy and optical measurements. The structural analyses reveal the existence of hexagonal CaSO{sub 4} phase with a (200) preferred orientation belonging to CaS compound for substrate temperatures below 350 °C. It is shown that the crystallinity of the sprayed thin films can be improved by increasing substrate temperature up to 250 °C. Warren-Averbach analysis has been applied on X-ray diffractogram to determine structural parameters involving the phase with its amount, the grain size and the lattice parameters using Maud software. The surface topography shows a rough surface covered by densely packed agglomerated clusters having faceted and hexagonal shapes. Energy dispersive microscopy measurements confirm the presence of calcium and sulfur in equal proportions as well as high percentage of oxygen. Photoluminescence at room temperature revealed that luminescence peaks are attributed to the intrinsic emission of pure CaSO{sub 4} phase. - Highlights: • Warren Averbach analysis reveal the presence of hcp structure of CaSO{sub 4} phase. • A mixture of CaSO{sub 4} and CaHO{sub 4.5}S phases has been detected for lower T{sub s}. • For increasing T{sub s}, the CaHO{sub 4.5}S phase has been disappeared. • The origin of PL peaks has been identified.

Samarium oxide as a radiotracer to evaluate the in vivo biodistribution of PLGA nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Mandiwana, Vusani, E-mail: VMandiwana@csir.co.za; Kalombo, Lonji, E-mail: LKalombo@csir.co.za [Centre of Polymers and Composites, CSIR (South Africa); Venter, Kobus, E-mail: Kobus.Venter@mrc.ac.za [South African Medical Research Council (South Africa); Sathekge, Mike, E-mail: Mike.Sathekge@up.ac.za [University of Pretoria and Steve Biko Academic Hospital, Department of Nuclear Medicine (South Africa); Grobler, Anne, E-mail: Anne.Grobler@nwu.ac.za; Zeevaart, Jan Rijn, E-mail: zeevaart@necsa.co.za [North-West University, DST/NWU Preclinical Drug Development Platform (South Africa)

2015-09-15

Developing nanoparticulate delivery systems that will allow easy movement and localization of a drug to the target tissue and provide more controlled release of the drug in vivo is a challenge in nanomedicine. The aim of this study was to evaluate the biodistribution of poly(d,l-lactide-co-glycolide) (PLGA) nanoparticles containing samarium-153 oxide ([{sup 153}Sm]Sm{sub 2}O{sub 3}) in vivo to prove that orally administered nanoparticles alter the biodistribution of a drug. These were then activated in a nuclear reactor to produce radioactive {sup 153}Sm-loaded-PLGA nanoparticles. The nanoparticles were characterized for size, zeta potential, and morphology. The nanoparticles were orally and intravenously (IV) administered to rats in order to trace their uptake through imaging and biodistribution studies. The {sup 153}Sm-loaded-PLGA nanoparticles had an average size of 281 ± 6.3 nm and a PDI average of 0.22. The zeta potential ranged between 5 and 20 mV. The [{sup 153}Sm]Sm{sub 2}O{sub 3} loaded PLGA nanoparticles, orally administered were distributed to most organs at low levels, indicating that there was absorption of nanoparticles. While the IV injected [{sup 153}Sm]Sm{sub 2}O{sub 3}-loaded PLGA nanoparticles exhibited the highest localization of nanoparticles in the spleen (8.63 %ID/g) and liver (3.07 %ID/g), confirming that nanoparticles are rapidly removed from the blood by the RES, leading to rapid uptake in the liver and spleen. From the biodistribution data obtained, it is clear that polymeric nanoscale delivery systems would be suitable for improving permeability and thus the bioavailability of therapeutic compounds.

Reductive Bis-addition of Aromatic Aldehydes to α,β-Unsaturated Esters via the Use of Sm/Cu(I) in Air: A Route to the Construction of Furofuran Lignans.

Science.gov (United States)

Liu, Yongjun; Tian, Guang; Li, Jingjing; Qi, Yan; Wen, Yonghong; Du, Feng

2017-06-02

The novel bis-addition of benzaldehydes to acrylates or maleates was achieved by the direct use of samarium metal with the assistance of CuI under mild conditions under dry air, and the useful 2-hydroxylalkyl-γ-butyrolactons and lignan derivatives were thus constructed with high efficiency. The key factors that influence the reaction efficiency were investigated. The use of potassium iodide and molecular sieves as additives can improve the reaction efficiency remarkably.

Honesty mediates the relationship between serotonin and reaction to unfairness.

Science.gov (United States)

Takahashi, Hidehiko; Takano, Harumasa; Camerer, Colin F; Ideno, Takashi; Okubo, Shigetaka; Matsui, Hiroshi; Tamari, Yuki; Takemura, Kazuhisa; Arakawa, Ryosuke; Kodaka, Fumitoshi; Yamada, Makiko; Eguchi, Yoko; Murai, Toshiya; Okubo, Yoshiro; Kato, Motoichiro; Ito, Hiroshi; Suhara, Tetsuya

2012-03-13

How does one deal with unfair behaviors? This subject has long been investigated by various disciplines including philosophy, psychology, economics, and biology. However, our reactions to unfairness differ from one individual to another. Experimental economics studies using the ultimatum game (UG), in which players must decide whether to accept or reject fair or unfair offers, have also shown that there are substantial individual differences in reaction to unfairness. However, little is known about psychological as well as neurobiological mechanisms of this observation. We combined a molecular imaging technique, an economics game, and a personality inventory to elucidate the neurobiological mechanism of heterogeneous reactions to unfairness. Contrary to the common belief that aggressive personalities (impulsivity or hostility) are related to the high rejection rate of unfair offers in UG, we found that individuals with apparently peaceful personalities (straightforwardness and trust) rejected more often and were engaged in personally costly forms of retaliation. Furthermore, individuals with a low level of serotonin transporters in the dorsal raphe nucleus (DRN) are honest and trustful, and thus cannot tolerate unfairness, being candid in expressing their frustrations. In other words, higher central serotonin transmission might allow us to behave adroitly and opportunistically, being good at playing games while pursuing self-interest. We provide unique neurobiological evidence to account for individual differences of reaction to unfairness.

The Role of Psychological Stress Reactions in the Longitudinal Relation Between Workplace Bullying and Turnover

DEFF Research Database (Denmark)

Nabe-Nielsen, Kirsten; Grynderup, Matias Brødsgaard; Conway, Paul Maurice

2017-01-01

OBJECTIVES: To investigate the association between workplace bullying and change of job/unemployment, and to investigate whether psychological stress reactions constitute a potential pathway linking workplace bullying and change of job/unemployment. METHODS: We used questionnaire data on workplace...... bullying and psychological stress reactions and register data on change of job/unemployment. We applied a multiple pathway approach to estimate the proportion of the association between workplace bullying and subsequent change of job/unemployment that was potentially mediated by psychological stress...... reactions. RESULTS: Workplace bullying was associated with risk of change of job (odds ratio [OR] = 1.35; 95% confidence interval [CI]: 1.06-1.72; 24% potentially mediated by psychological stress reactions) and unemployment (OR = 4.90; 95% CI: 3.18-7.55; 19% potentially mediated by psychological stress...

Enzyme mediated synthesis of polypyrrole in the presence of chondroitin sulfate and redox mediators of natural origin

International Nuclear Information System (INIS)

Grijalva-Bustamante, G.A.; Evans-Villegas, A.G.; Castillo-Castro, T. del; Castillo-Ortega, M.M.; Cruz-Silva, R.; Huerta, F.; Morallón, E.

2016-01-01

Polypyrrole (PPy) was synthesized by enzyme mediated oxidation of pyrrole using naturally occurring compounds as redox mediators. The catalytic mechanism is an enzymatic cascade reaction in which hydrogen peroxide is the oxidizer and soybean peroxidase, in the presence of acetosyringone, syringaldehyde or vanillin, acts as a natural catalysts. The effect of the initial reaction composition on the polymerization yield and electrical conductivity of PPy was analyzed. Morphology of the PPy particles was studied by scanning electron microscopy and transmission electron microscopy whereas the chemical structure was studied by X-ray photoelectron and Fourier transformed infrared spectroscopic techniques. The redox mediators increased the polymerization yield without a significant modification of the electronic structure of PPy. The highest conductivity of PPy was reached when chondroitin sulfate was used simultaneously as dopant and template during pyrrole polymerization. Electroactive properties of PPy obtained from natural precursors were successfully used in the amperometric quantification of uric acid concentrations. PPy increases the amperometric sensitivity of carbon nanotube screen-printed electrodes toward uric acid detection. - Highlights: • A new method of pyrrole polymerization using naturally occurring redox mediators and doping agents was studied. • The catalytic efficiency of different redox mediators toward pyrrole oxidation was evaluated. • Two different naturally occurring polymers were studied as bifunctional steric stabilizer/doping agents. • Polypyrrole improves the amperometric response of carbon nanotube screen printed electrodes toward uric acid sensing.

Enzyme mediated synthesis of polypyrrole in the presence of chondroitin sulfate and redox mediators of natural origin

Energy Technology Data Exchange (ETDEWEB)

Grijalva-Bustamante, G.A. [Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Evans-Villegas, A.G. [Departamento de Ciencias Químico Biológicas, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Castillo-Castro, T. del, E-mail: terecat@polimeros.uson.mx [Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Castillo-Ortega, M.M. [Departamento de Investigación en Polímeros y Materiales, Universidad de Sonora, CP 83000 Hermosillo, Sonora (Mexico); Cruz-Silva, R. [Research Center for Exotic Nanocarbons, Shinshu University, 4-17-1 Wakasato, 380-8553, Nagano (Japan); Huerta, F. [Departamento Ingeniería Textil y Papelera, Universitat Politecnica de Valencia, Plaza Ferrandiz y Carbonell, 1, E-03801 Alcoy (Spain); Morallón, E. [Departamento Química Física e Instituto Universitario de Materiales, Universidad de Alicante, Ap. 99, E-03080 Alicante (Spain)

2016-06-01

Polypyrrole (PPy) was synthesized by enzyme mediated oxidation of pyrrole using naturally occurring compounds as redox mediators. The catalytic mechanism is an enzymatic cascade reaction in which hydrogen peroxide is the oxidizer and soybean peroxidase, in the presence of acetosyringone, syringaldehyde or vanillin, acts as a natural catalysts. The effect of the initial reaction composition on the polymerization yield and electrical conductivity of PPy was analyzed. Morphology of the PPy particles was studied by scanning electron microscopy and transmission electron microscopy whereas the chemical structure was studied by X-ray photoelectron and Fourier transformed infrared spectroscopic techniques. The redox mediators increased the polymerization yield without a significant modification of the electronic structure of PPy. The highest conductivity of PPy was reached when chondroitin sulfate was used simultaneously as dopant and template during pyrrole polymerization. Electroactive properties of PPy obtained from natural precursors were successfully used in the amperometric quantification of uric acid concentrations. PPy increases the amperometric sensitivity of carbon nanotube screen-printed electrodes toward uric acid detection. - Highlights: • A new method of pyrrole polymerization using naturally occurring redox mediators and doping agents was studied. • The catalytic efficiency of different redox mediators toward pyrrole oxidation was evaluated. • Two different naturally occurring polymers were studied as bifunctional steric stabilizer/doping agents. • Polypyrrole improves the amperometric response of carbon nanotube screen printed electrodes toward uric acid sensing.

Fabrication of samarium strontium aluminate ceramic and deposition of thermal barrier coatings by air plasma spray process

Directory of Open Access Journals (Sweden)

Baskaran T

2018-01-01

Full Text Available Thermal barrier coatings (TBC with the metallic NiCrAlY bond coat are often used in many aircraft engines to protect superalloy components from high-temperature corrosion thereby to improve the life of gas turbine components. The search for new TBC material has been intensified in recent years due to lack of thermo-physical properties of conventionally used Yttria stabilized Zirconia (YSZ TBCs. Recently, the rare earth containing Samarium Strontium Aluminate (SSA based ceramic was proposed as a new TBC material due to its matching thermo-physical properties with the substrate. The present work focused on the synthesis of SSA ceramics for TBCs application and its coatings development on Ni-based superalloy Inconel 718 substrate by air plasma spray process. The X-ray photoelectron spectroscopy (XPS result confirmed the formation of single phase SSA ceramic after synthesis. The surface morphology of SSA TBCs is mainly composed of melted splats, semi and un-melted particles. The cross-sectional SEM micrographs did not show any spallation at the interface which indicated good mechanical interlocking between the bond coat and ceramic top coat. The Young’s modulus and hardness of SSA TBCs were found to be 80 and 6.1 GPa, respectively. The load-depth curve of SSA TBC showed good elastic recovery about 47 %.

Synthesis and Purification of Iodoaziridines Involving Quantitative Selection of the Optimal Stationary Phase for Chromatography

Science.gov (United States)

Boultwood, Tom; Affron, Dominic P.; Bull, James A.

2014-01-01

The highly diastereoselective preparation of cis-N-Ts-iodoaziridines through reaction of diiodomethyllithium with N-Ts aldimines is described. Diiodomethyllithium is prepared by the deprotonation of diiodomethane with LiHMDS, in a THF/diethyl ether mixture, at -78 °Cin the dark. These conditions are essential for the stability of the LiCHI2 reagent generated. The subsequent dropwise addition of N-Ts aldimines to the preformed diiodomethyllithium solution affords an amino-diiodide intermediate, which is not isolated. Rapid warming of the reaction mixture to 0 °C promotes cyclization to afford iodoaziridines with exclusive cis-diastereoselectivity. The addition and cyclization stages of the reaction are mediated in one reaction flask by careful temperature control. Due to the sensitivity of the iodoaziridines to purification, assessment of suitable methods of purification is required. A protocol to assess the stability of sensitive compounds to stationary phases for column chromatography is described. This method is suitable to apply to new iodoaziridines, or other potentially sensitive novel compounds. Consequently this method may find application in range of synthetic projects. The procedure involves firstly the assessment of the reaction yield, prior to purification, by 1H NMR spectroscopy with comparison to an internal standard. Portions of impure product mixture are then exposed to slurries of various stationary phases appropriate for chromatography, in a solvent system suitable as the eluent in flash chromatography. After stirring for 30 min to mimic chromatography, followed by filtering, the samples are analyzed by 1H NMR spectroscopy. Calculated yields for each stationary phase are then compared to that initially obtained from the crude reaction mixture. The results obtained provide a quantitative assessment of the stability of the compound to the different stationary phases; hence the optimal can be selected. The choice of basic alumina, modified to

Agmatine, an endogenous ligand at imidazoline binding sites, does not antagonize the clonidine-mediated blood pressure reaction

Science.gov (United States)

Raasch, Walter; Schäfer, Ulrich; Qadri, Fatimunnisa; Dominiak, Peter

2002-01-01

Since agmatine has been identified as a clonidine displacing substance (CDS), the aim of this study was to investigate whether agmatine can mimic CDS-induced cardiovascular reactions in organ bath experiments, pithed spontaneously hypertensive rats (SHR) and anaesthetized SHR.Intravenously-administered agmatine significantly reduced the blood pressure and heart rate of anaesthetized SHR at doses higher than 1 and 3 mg kg−1, respectively. These effects are probably mediated via central mechanisms, since there was an approximate 8 fold rightward shift of the dose-response curve in the pithed SHR (indicating a weakened cardiovascular effect). Moreover, in organ bath experiments, agmatine failed to alter the contractility of intact or endothelium-denuded aortal rings. When agmatine was administered i.c.v. to anaesthetized SHR, blood pressure was increased without any alteration of heart rate, whereas blood pressure was unchanged and heart rate was increased after injection into the 4th brain ventricle. This suggests that haemodynamic reaction patterns after central application are related to distinct influences on central cardiovascular mechanisms.Agmatine reduces noradrenaline release in pithed SHR while α2-adrenoceptors are irreversibly blocked with phenoxybenzamine, but not while I1-binding sites are selectively blocked with AGN192403. This suggests that agmatine may modulate noradrenaline release in the same way that clonidine does, i.e. via imidazoline binding sites; this involves a reduction in sympathetic tone which in turn reduces blood pressure and heart rate.Finally, CDS-like cardiovascular activity appears not to be due to agmatine, since (i) blood pressure in anaesthetized SHR is decreased by agmatine and clonidine, and (ii) agmatine did not antagonize the blood pressure reaction to clonidine in pithed or anaesthetized SHR. PMID:11834614

Time Course of Detection of Human Male DNA from Stained Blood Sample on Various Surfaces by Loop Mediated Isothermal Amplification and Polymerase Chain Reaction

OpenAIRE

Panan Kanchanaphum

2018-01-01

This study explores determining the sex of humans from blood stains taken from different surfaces and compares the time course of detection with the conventional PCR, Conventional Loop Mediated Isothermal Amplification (LAMP), and LAMP-Lateral Flow Dipstick (LFD). For the DNA templates, 7 male and 7 female blood stained samples were extracted and added to LAMP and PCR reaction solution to amplify the SRY gene. The DNA samples were extracted from the following blood stained materials: cloth, w...

Quantitative DFT modeling of product concentration in organometallic reactions: Cu-mediated pentafluoroethylation of benzoic acid chlorides as a case study.

Science.gov (United States)

Jover, Jesús

2017-11-08

DFT calculations are widely used for computing properties, reaction mechanisms and energy profiles in organometallic reactions. A qualitative agreement between the experimental and the calculated results seems to usually be enough to validate a computational methodology but recent advances in computation indicate that a nearly quantitative agreement should be possible if an appropriate DFT study is carried out. Final percent product concentrations, often reported as yields, are by far the most commonly reported properties in experimental metal-mediated synthesis studies but reported DFT studies have not focused on predicting absolute product amounts. The recently reported stoichiometric pentafluoroethylation of benzoic acid chlorides (R-C 6 H 4 COCl) with [(phen)Cu(PPh 3 )C 2 F 5 ] (phen = 1,10-phenanthroline, PPh 3 = triphenylphosphine) has been used as a case study to check whether the experimental product concentrations can be reproduced by any of the most popular DFT approaches with high enough accuracy. To this end, the Gibbs energy profile for the pentafluoroethylation of benzoic acid chloride has been computed using 14 different DFT methods. These computed Gibbs energy profiles have been employed to build kinetic models predicting the final product concentration in solution. The best results are obtained with the D3-dispersion corrected B3LYP functional, which has been successfully used afterwards to model the reaction outcomes of other simple (R = o-Me, p-Me, p-Cl, p-F, etc.) benzoic acid chlorides. The product concentrations of more complex reaction networks in which more than one position of the substrate may be activated by the copper catalyst (R = o-Br and p-I) are also predicted appropriately.

Silica Gel-Mediated Organic Reactions under Organic Solvent-Free Conditions

Directory of Open Access Journals (Sweden)

Satoaki Onitsuka

2012-09-01

Full Text Available Silica gel was found to be an excellent medium for some useful organic transformations under organic solvent-free conditions, such as (1 the Friedel-Crafts-type nitration of arenes using commercial aqueous 69% nitric acid alone at room temperature, (2 one-pot Wittig-type olefination of aldehydes with activated organic halides in the presence of tributyl- or triphenylphosphine and Hunig’s base, and (3 the Morita-Baylis-Hillman reaction of aldehydes with methyl acrylate. After the reactions, the desired products were easily obtained in good to excellent yields through simple manipulation.

Laccase/Mediator Systems: Their Reactivity toward Phenolic Lignin Structures.

Science.gov (United States)

Hilgers, Roelant; Vincken, Jean-Paul; Gruppen, Harry; Kabel, Mirjam A

2018-02-05

Laccase-mediator systems (LMS) have been widely studied for their capacity to oxidize the nonphenolic subunits of lignin (70-90% of the polymer). The phenolic subunits (10-30% of the polymer), which can also be oxidized without mediators, have received considerably less attention. Consequently, it remains unclear to what extent the presence of a mediator influences the reactions of the phenolic subunits of lignin. To get more insight in this, UHPLC-MS was used to study the reactions of a phenolic lignin dimer (GBG), initiated by a laccase from Trametes versicolor , alone or in combination with the mediators HBT and ABTS. The role of HBT was negligible, as its oxidation by laccase occurred slowly in comparison to that of GBG. Laccase and laccase/HBT oxidized GBG at a comparable rate, resulting in extensive polymerization of GBG. In contrast, laccase/ABTS converted GBG at a higher rate, as GBG was oxidized both directly by laccase but also by ABTS radical cations, which were rapidly formed by laccase. The laccase/ABTS system resulted in Cα oxidation of GBG and coupling of ABTS to GBG, rather than polymerization of GBG. Based on these results, we propose reaction pathways of phenolic lignin model compounds with laccase/HBT and laccase/ABTS.

Coherent and semi-coherent neutron transfer reactions

International Nuclear Information System (INIS)

Hagelstein, P.L.

1992-01-01

Neutron transfer reactions are proposed to account for anomalies reported in Pons-Fleischmann experiments. The prototypical reaction involves the transfer of a neutron (mediated by low frequency electric or magnetic fields) from a donor nucleus to virtual continuum states, followed by the capture of the virtual neutron by an acceptor nucleus. In this work we summarize basic principles, recent results and the ultimate goals of the theoretical effort

Coherent and semi-coherent neutron transfer reactions

International Nuclear Information System (INIS)

Hagelstein, P.L.

1993-01-01

Neutron transfer reactions are proposed to account for anomalies reported in Pons-Fleischmann experiments. The prototypical reaction involves the transfer of a neutron (mediated by low frequency electric or magnetic fields) from a donor nucleus to virtual continuum states, followed by the capture of the virtual neutron by an acceptor nucleus. In this work we summarize basic principles, recent results and the ultimate goals of the theoretical effort. (author)

Immediate and delayed cutaneous reactions to radiocontrast media.

Science.gov (United States)

Brockow, Knut

2012-01-01

Hypersensitivity reactions to contrast media (CM) are frequent causes of anaphylaxis and drug exanthemas. Adverse events after CM exposure are classified into immediate (≤1 h) and non-immediate reactions (>1 h), with differing mechanisms. In the majority of patients with immediate reactions, IgE-mediated allergy cannot be demonstrated, and the underlying mechanism remains unknown. However, recent data have provided evidence for skin test positivity and/or specific IgE in some patients. T cell-mediated hypersensitivity is the responsible mechanism for the majority of non-immediate skin eruptions. These insights have consequences for diagnosis and prevention. Skin testing evolves to be a useful tool for diagnosis of CM allergy. Skin tests have been employed to confirm this hypersensitivity. Previous reactors have an increased risk to develop new reactions upon repeated exposure; however, other risk factors are poorly defined. The use of skin tests for the selection of a 'safe' CM is under investigation with promising results. In vitro tests to search for CM-specific cell activation include flow cytometric approaches, lymphocyte cultures and construction of cell lines and hybridomas. Premedication of previous reactors is common practice among radiologists; however, breakthrough reactions are a concern, and physicians should not rely on the efficacy of pharmacological premedication. Copyright © 2012 S. Karger AG, Basel.

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads.

Science.gov (United States)

Niemi, Marja; Tkachenko, Nikolai V; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-07-31

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results in rapid ET from phthalocyanine to fullerene via an exciplex state in both polar and nonpolar solvents. Relaxation of the charge-separated (CS) state Pc(*+)-C60(*-) in a polar solvent occurs directly to the ground state in 30-70 ps. In a nonpolar solvent, roughly 20% of the molecules undergo transition from the CS state to phthalocyanine triplet state (3)Pc*-C60 before relaxation to the ground state. Formation of the CS state was confirmed with electron spin resonance measurements at low temperature in both polar and nonpolar solvent. Reaction schemes for the photoinduced ET reactions of the dyads were completed with rate constants obtained from the time-resolved absorption and emission measurements and with state energies obtained from the fluorescence, phosphorescence, and voltammetric measurements.

The relative role of cognitive and emotional reactions in mediating the effects of a social comparison sun protection intervention.

Science.gov (United States)

Mahler, Heike I M

2018-02-01

This experiment examined the cognitive and emotional impact of two social comparison-based sun protection interventions in a sample of Southern California college students (N = 223). One of the interventions employed comparison UV photos of peers who had either much more (downward social comparison) or much less (upward social comparison) skin damage than did participants themselves. The second intervention consisted of descriptive norms information suggesting that a large majority of the participants' peer group regularly protect their skin from the sun. Participants were randomly assigned to one of eight conditions in a 4 (Social Comparison Information: no photo vs. no comparison photos vs. upward comparison photos vs. downward comparison photos) × 2 (Descriptive Norms Information: Received vs. not received) design. Emotional reactions (e.g. worry, embarrassment, relief) and sun-related cognitive reactions (perceived susceptibility, sun protection intentions) were assessed immediately. Sun protection behaviours were assessed in a surprise telephone follow-up five weeks following the intervention. The results demonstrated that the combination of seeing photos of peers who had very little sun damage and learning that a majority of one's peers engage in regular sun protection resulted in reliably greater subsequent sun protection than all other conditions. Further, there was relatively direct evidence that both negative emotional reactions and sun protection intentions mediated this effect. These findings add to the growing literature suggesting the importance of thoroughly examining the role of emotions in health behaviour decisions. Both theory and intervention efficacy would benefit from a better understanding of the relative role of cognitions and emotions in behaviour change.

Laccase/mediator assisted degradation of triarylmethane dyes in a continuous membrane reactor.

Science.gov (United States)

Chhabra, Meenu; Mishra, Saroj; Sreekrishnan, Trichur Ramaswamy

2009-08-10

Laccase/mediator systems are important bioremediation agents as the rates of reactions can be enhanced in the presence of the mediators. The decolorization mechanism of two triarylmethane dyes, namely, Basic Green 4 and Acid Violet 17 is reported using Cyathus bulleri laccase. Basic Green 4 was decolorized through N-demethylation by laccase alone, while in mediator assisted reactions, dye breakdown was initiated from oxidation of carbinol form of the dye. Benzaldehyde and N,N-dimethyl aniline were the major end products. With Acid Violet 17, laccase carried out N-deethylation and in mediator assisted reactions, oxidation of the carbinol form of the dye occurred resulting in formation of formyl benzene sulfonic acid, carboxy benzene sulfonic acid and benzene sulfonic acid. Toxicity analysis revealed that Basic Green 4 was toxic and treatment with laccase/mediators resulted in 80-100% detoxification. The treatment of the textile dye solution using laccase and 2,2'-azino-di-(-ethylbenzothiazoline-6-sulfonic acid) (ABTS) was demonstrated in an enzyme membrane reactor. At a hydraulic retention time of 6h, the process was operated for a period of 15 days with nearly 95% decolorization, 10% reduction in flux and 70% recovery of active ABTS.

Large local reactions to insect stings.

Science.gov (United States)

Golden, David B K

2015-01-01

Large local reactions (LLRs) are IgE-mediated late-phase inflammatory reactions that can cause great morbidity but are associated with a relatively low risk of future anaphylaxis. Patients with LLR may benefit from consultation with an allergist to help clarify the relative risk, to plan the best treatment for future stings, and to determine whether or not to pursue testing or venom immunotherapy (VIT). The chance of anaphylaxis to future stings is Immunology. Published by Elsevier Inc. All rights reserved.

The effectiveness of samarium-153 (153Sm) lexidronam (EDTMP) in treatment of bone metastases

International Nuclear Information System (INIS)

Ma Yubo; Huang Gang; Liu Jianjun

2004-01-01

Objectives: To evaluate the effectiveness of samarium-153 (153Sm) lexidronam (EDTMP) in treatment of bone metastases. Methods: 380 patients with bone metastases were studied (221 men, 159 women; average age 65.3 y; ranged 27-91 y; average weight 59.3 kg, ranged 39-95 kg). The tumor types were prostate carcinoma (n=155), pulmonary carcinoma (n=92), breast cancer (n=57), gastric carcinoma (n=12), colorectal carcinoma (n=22), nasopharyngeal carcinoma (n=8), lymphoma (n=8), hepatic carcinoma (n=6), ovary carcinoma (n=4) and others (n=16). All patients were received 135Sm-EDTMP 0.8 or 1.0 mCi/kg during 1 to 7 course of treatment. Patients and physician evaluations were used to assess pain relief. Numbers of metastatic foci and activity of ROIs were used to observe post-therapy change in bone scanning. Results: In 380 patients, pain relief was observed in 257 patients (67.6%). Persistence of pain relief was seen through 2 to 24 weeks. The mean relief time is 5.8±3.4 weeks. KPS score was higher 10% than pre-therapy (71.2%±9.6% Vs 80.9%±10.3%, p<0.001). Numbers of metastatic foci (11.2+8.8 Vs 8.4±5.7, p<0.001) and activity of ROIs (3.28±2.04 Vs 2.15±0.94, p<0.01) were less than pre-therapy. Bone marrow suppression was mild and reversible (5.87±1.56 Vs 4.94±1.16 x 109/L). Conclusions: 153Sm-EDTMP provided relief of pain associated with bone metastases and inhibition of metastatic foci. As a relief drug of painful bone metastases, 153Sm-EDTMP is safe and effective. (authors)

Mediator profiles in tears during the conjunctival response induced by allergic reaction in the nasal mucosa.

Science.gov (United States)

Pelikan, Zdenek

2013-01-01

The allergic reaction occurring primarily in the nasal mucosa can induce a secondary conjunctival response of an immediate (SICR), late (SLCR), or delayed (SDYCR) type in some patients with allergic conjunctivitis (AC). To investigate the concentration changes of histamine, tryptase, eosinophil cationic protein (ECP), eosinophil-derived neurotoxin (EDN), leukotrienes (LTB 4, LTC4, LTE4), myeloperoxidase (MPO), interferon-γ (IFN-γ), and interleukins (IL-2, IL-4, IL-5) in tears during the SICR, SLCR, and SDYCR. In 32 patients with AC, 11 SICR (ptears. The SICRs were associated with significant concentration changes in tears (ptears (ptears during the 32 PBS controls (p>0.1) or in the ten control patients (p>0.1). These results provide evidence for causal involvement of nasal allergy in some patients with AC, inducing secondary conjunctival response of immediate (SICR), late SLCR, or delayed SDYCR type, associated with different mediator, cytokine, and cellular profiles in the tears, suggesting involvement of different hypersensitivity mechanisms. These results also emphasize the diagnostic value of nasal allergen challenge combined with monitoring of the conjunctival response in some patients with AC.

Determination of the speciation and bioavailability of samarium to Chlamydomonas reinhardtii in the presence of natural organic matter.

Science.gov (United States)

Rowell, Justine-Anne; Fillion, Marc-Alexandre; Smith, Scott; Wilkinson, Kevin J

2018-06-01

As technological interest and environmental emissions of the rare earth elements increase, it is becoming more important to assess their potential environmental impact. Samarium (Sm) is a lanthanide of intermediate molar mass that is used in numerous high-technology applications including wind turbines, solar panels, and electric vehicles. The present study relates the speciation of Sm determined in the presence of natural organic matter (NOM) to its bioavailability to the unicellular green alga Chlamydomonas reinhardtii. The free ion concentration was determined using a cation exchange resin (ion exchange technique) in dynamic mode and compared with thermodynamic modeling. Short-term biouptake experiments were performed in the presence of 4 types of NOM: Suwannee River fulvic acids, Pahokee Peat fulvic acids, Suwannee River humic acids, and a Luther Marsh dissolved organic matter isolate (90-95% humic acids). It was clearly shown that even a small amount of NOM (0.5 mg C L -1 ) resulted in a significant decrease (10 times) in the Sm internalization fluxes. Furthermore, complexation with humic acids (and the corresponding reduction in Sm bioavailability) was stronger than that with fulvic acids. The results showed that the experimentally measured (free) Sm was a better predictor of Sm internalization than either the total concentrations or the free ion concentrations obtained using thermodynamic modeling. Environ Toxicol Chem 2018;37:1623-1631. © 2018 SETAC. © 2018 SETAC.

Dynamics of anion-molecule reactions at low energy

International Nuclear Information System (INIS)

Mikosch, J.

2007-11-01

Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S N 2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S N 2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S N 2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S N 2 mechanism involving CH 3 -rotation. (orig.)

Dynamics of anion-molecule reactions at low energy

Energy Technology Data Exchange (ETDEWEB)

Mikosch, J.

2007-11-15

Anion-molecule reactions must find their way through deeply bound entrance and exit channel complexes separated by a central barrier. This results in low reaction rates and rich dynamics since direct pathways compete with the formation of transient intermediates. In this thesis we examine the probability of proton transfer to a small anion and transient lifetimes of a thermoneutral bimolecular nucleophilic substitution (S{sub N}2) reaction at well defined variable temperature down to 8 Kelvin in a multipole trap. The observed strong inverse temperature dependence is attributed to the deficit of available quantum states in the entrance channel at decreasing temperature. Furthermore we investigate scattering dynamics of S{sub N}2 reactions at defined relative energy between 0.4 and 10 eV by crossed beam slice imaging. A weakly exothermic reaction with high central barrier proceeds via an indirect, complex-mediated mechanism at low relative energies featuring high internal product excitation in excellent quantitative agreement with a statistical model. In contrast, direct backward scattering prevails for higher energies with product velocities close to the kinematical cutoff. For a strongly exothermic reaction, competing S{sub N}2-, dihalide- and proton transfer-channels are explored which proceed by complex mediation for low energy and various rebound-, grazing- and collision induced bond rupture-mechanisms at higher energy. From our data and a collaboration with theory we identify a new indirect roundabout S{sub N}2 mechanism involving CH{sub 3}-rotation. (orig.)

Samarium-153 Oksabifor in the treatment of metastatic bone disease

International Nuclear Information System (INIS)

Solodyannikova, O.; Voit, N.; Sukach, G.; Sagan, D.

2015-01-01

patients - reducing the number of foci and the level of radiopharmaceutical uptake in them. Conclusions: radionuclide therapy in patients with BM can effectively suppress pain and significantly reduce the number of analgesics. Post-treatment patients, life quality statistically significantly improved. Samarium-153 has the ability to reduce BM number and intensity of radiopharmaceutical accumulation in spots in the control study. (authors)

Why is discrimination stressful? The mediating role of cognitive appraisal.

Science.gov (United States)

King, Kimberly R

2005-08-01

This study attempts to shed light on past findings that experiences of racial and gender discrimination are associated with poor psychological and physical health outcomes by investigating the role of cognitive appraisal as a mediator of the relationship between experiences of discrimination and affective stress reactions. African American female college students (N = 115) imagined themselves in an audiotaped scenario in which they overheard 2 European American male classmates make negative evaluations of them. Participants then completed measures of causal attributions, cognitive appraisal, and affective stress reactions. Multiple regression analyses supported the hypotheses that attributions to racism and to discrimination that combines racism and sexism were associated with increased stress reactions. This relationship was mediated by cognitive appraisals of centrality. (c) 2005 APA

Fluorescence properties of europium and samarium. beta. -diketonates and their use in fluorometry

Energy Technology Data Exchange (ETDEWEB)

Huang, H; Hiraki, K; Nishikawa, Y [Kinki Univ., Higashi-Osaka, Osaka (Japan). Faculty of Science and Technology

1981-01-01

Several europium and samarium ..beta..-diketonates (tta, ntfa, bfa) complexed with 1, 10-phenanthroline, or with trioctylphosphine oxide (topo) were synthesized. The fluorescence properties of these compounds in benzene or hexane have been studied. Absorption and fluorescence spectra, fluorescence quantum yield, fluorescence sensitivity index (F.S.I.), and fluorescence lifetime were measured. From the measurement of fluorescence lifetime of the ..beta..-diketonates, the velocity of radiative process (k sub(f)/phi sub(f)) has almost the same value for benzene and hexane solvent. The red fluorescence (Em. max. : 619 nm) of Eu(III) in these chelates is attributed to transitions from /sup 5/D/sub 0/ ..-->.. /sup 7/F/sub 2/ levels of this ion, and the three-band spectrum (Em. max. : 569 nm, 606 nm, 650 nm) indicates the transitions from the /sup 4/G sub(5/2) ..-->.. /sup 6/H sub(5/2), /sup 4/G sub(5/2) ..-->.. /sup 6/H sub(7/2), and /sup 4/G sub(5/2) ..-->.. /sup 6/H sub(9/2) levels of Sm(III), respectively. These spectra are not changed by any solvents and ligands. From the results, the fluorescence of the ..beta..-diketonates in organic solvent has been attributed to m* ..-->.. m luminescence transition. The complexes of Eu(III) and Sm(III) show radiative transition within orbitals, composed exclusively of 4f orbitals of rare earth ions (m* ..-->.. m radiative transition). Fluorinated ligands show better sensitivity than unfluorinated ligands, and the best sensitivity is obtained with TTA-phen system, and/or TTA-topo system for the spectrofluorometric determination of the two metals. In the case of Eu determination, 619 nm emission wavelength is used (the determinable range : 0.2 -- 10 ppb Eu), and in the case of Sm determination, 650 nm emission wavelength is adopted (the determinable range : 0.1 -- 1 ppm Sm), because of much higher sensitivity than the other two peaks (569, 606 nm) without interference from europium complex.

The development of CotA mediator cocktail system for dyes decolorization.

Science.gov (United States)

Luo, S; Xie, T; Liu, Z; Sun, F; Wang, G

2018-05-01

The increasing use of dyes leads to serious environmental concerns, it is significant to explore eco-friendly and economic approaches for dye decolorization. This study aimed to develop mediator cocktail (AS and ABTS) for enhancing the capability of laccase-mediator system in the removal of dyes. By mediator screening, the mediators of ABTS and AS (ABTS, 2, 2'-azino-bis-(3-ethylbenzothiazo-thiazoline-6-sulphonic acid); AS, acetosyringone) were combined for dyes decolorization. The Box-Behnken Design and response surface analysis was performed to optimize experiment conditions. Comparing the CotA-ABTS-AS cocktail system with CotA-single mediator system showed that the coupling of ABTS and AS could increase the decolorization rate 15 times higher, save a third of the cost and shorten the reaction time by 50%. In addition, our studies revealed that sequential oxidation may occur in CotA-ABTS-AS system. Compared with CotA laccase-single mediator system, the CotA-ABTS-AS cocktail system showed advantages including higher efficiency, lower cost and shorter reaction time. This was the first report on the dyes decolorization by laccase mediator cocktail system. These results paved the curb for the application of laccase mediator system in various industrial processes. © 2018 The Society for Applied Microbiology.

Real-time observation of intersystem crossing induced by charge recombination during bimolecular electron transfer reactions

KAUST Repository

Alsam, Amani Abdu

2016-09-21

Real-time probing of intersystem crossing (ISC) and triplet-state formation after photoinduced electron transfer (ET) is a particularly challenging task that can be achieved by time-resolved spectroscopy with broadband capability. Here, we examine the mechanism of charge separation (CS), charge recombination (CR) and ISC of bimolecular photoinduced electron transfer (PET) between poly[(9,9-di(3,3′-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and dicyanobenzene (DCB) using time-resolved spectroscopy. PET from PFN to DCB is confirmed by monitoring the transient absorption (TA) and infrared spectroscopic signatures for the radical ion pair (DCB─•-PFN+•). In addition, our time-resolved results clearly demonstrate that CS takes place within picoseconds followed by CR within nanoseconds. The ns-TA data exhibit the clear spectroscopic signature of PFN triplet-triplet absorption, induced by the CR of the radical ion pairs (DCB─•-PFN+•). As a result, the triplet state of PFN (3PFN*) forms and subsequently, the ground singlet state is replenished within microseconds. © 2016

Molecular controls of the oxygenation and redox reactions of hemoglobin.

Science.gov (United States)

Bonaventura, Celia; Henkens, Robert; Alayash, Abdu I; Banerjee, Sambuddha; Crumbliss, Alvin L

2013-06-10

The broad classes of O(2)-binding proteins known as hemoglobins (Hbs) carry out oxygenation and redox functions that allow organisms with significantly different physiological demands to exist in a wide range of environments. This is aided by allosteric controls that modulate the protein's redox reactions as well as its O(2)-binding functions. The controls of Hb's redox reactions can differ appreciably from the molecular controls for Hb oxygenation and come into play in elegant mechanisms for dealing with nitrosative stress, in the malarial resistance conferred by sickle cell Hb, and in the as-yet unsuccessful designs for safe and effective blood substitutes. An important basic principle in consideration of Hb's redox reactions is the distinction between kinetic and thermodynamic reaction control. Clarification of these modes of control is critical to gaining an increased understanding of Hb-mediated oxidative processes and oxidative toxicity in vivo. This review addresses emerging concepts and some unresolved questions regarding the interplay between the oxygenation and oxidation reactions of structurally diverse Hbs, both within red blood cells and under acellular conditions. Developing methods that control Hb-mediated oxidative toxicity will be critical to the future development of Hb-based blood substitutes.

Modelling Toehold-Mediated RNA Strand Displacement

OpenAIRE

Šulc, Petr; Ouldridge, Thomas E.; Romano, Flavio; Doye, Jonathan P.K.; Louis, Ard A.

2015-01-01

We study the thermodynamics and kinetics of an RNA toehold-mediated strand displacement reaction with a recently developed coarse-grained model of RNA. Strand displacement, during which a single strand displaces a different strand previously bound to a complementary substrate strand, is an essential mechanism in active nucleic acid nanotechnology and has also been hypothesized to occur in vivo. We study the rate of displacement reactions as a function of the length of the toehold and temperat...

Singlet oxygen-mediated damage to proteins and its consequences

DEFF Research Database (Denmark)

Davies, Michael Jonathan

2003-01-01

by the transfer of energy to ground state (triplet) molecular oxygen by either protein-bound, or other, chromophores. Singlet oxygen can also be generated by a range of other enzymatic and non-enzymatic reactions including processes mediated by heme proteins, lipoxygenases, and activated leukocytes, as well...... the absorption of UV radiation by the protein, or bound chromophore groups, thereby generating excited states (singlet or triplets) or radicals via photo-ionisation. The second major process involves indirect oxidation of the protein via the formation and subsequent reactions of singlet oxygen generated...... as radical termination reactions. This paper reviews the data available on singlet oxygen-mediated protein oxidation and concentrates primarily on the mechanisms by which this excited state species brings about changes to both the side-chains and backbone of amino acids, peptides, and proteins. Recent work...

The effect of caffeine to increase reaction time in the rat during a test of attention is mediated through antagonism of adenosine A2A receptors.

Science.gov (United States)

Higgins, Guy A; Grzelak, Michael E; Pond, Annamarie J; Cohen-Williams, Mary E; Hodgson, Robert A; Varty, Geoffrey B

2007-12-11

Caffeine produces effects on cognitive function particularly relating to aspects of attention such as reaction time. Considering the plasma exposure levels following regular caffeine intake, and the affinity of caffeine for known protein targets, these effects are likely mediated by either the adenosine A(1) or A(2A) receptor. In the present studies, two rat strains [Long-Evans (LE) and CD] were trained to asymptote performance in a test of selective attention, the 5-choice serial reaction time task (5-CSRTT). Next, the effects of caffeine were compared to the selective A(2A) antagonists, SCH 412348 and KW-6002 (Istradefylline), and the A(1) antagonist, DPCPX. Further studies compared the psychostimulant effects of each drug. Finally, we tested the A(2A) agonist, CGS-21680, on 5-CSRTT performance and given the antipsychotic potential of this drug class, studied the interaction between CGS-21680 and amphetamine in this task. Caffeine (3-10mg/kg IP) increased reaction time in both LE and CD rats, with no effect on accuracy, an effect replicated by SCH 412348 (0.1-1mg/kg PO) and KW-6002 (1-3mg/kg PO), but not DPCPX (3-30 mg/kg PO). At least with SCH 412348, these effects were at doses that were not overtly psychostimulant. In contrast, CGS-21680 (0.03-0. 3mg/kg IP) slowed reaction speed and increased omissions. Interestingly, at a comparatively low dose of 0.03 mg/kg, CGS-21680 attenuated the increased premature responding produced by amphetamine (1mg/kg IP). The present results suggest that the attention-enhancing effects of caffeine are mediated through A(2A) receptor blockade, and selective A(2A) receptor antagonists may have potential as therapies for attention-related disorders. Furthermore, the improvement in response control in amphetamine-treated rats following CGS-21680 pretreatment supports the view that A(2A) agonists have potential as novel antipsychotics.

Isotopic studies on oxidative methane coupling over samarium oxide

International Nuclear Information System (INIS)

Otsuka, Kiyoshi; Inaida, Masakatsu; Wada, Yuji; Komatsu, Takayuki; Morikawa, Akira

1989-01-01

The evident kinetic isotope effect was observed for the formations of ethylene and ethane through the oxidative coupling of methane on Sm 2 O 3 , when CH 4 and CD 4 were used as the reactants. Ethanes formed in the reaction of a mixture of CH 4 , CD 4 , and O 2 were C 2 H 6 , C 2 H 3 D 3 , and C 2 D 6 as major products. These results indicate that the rate-determining step of the reaction is abstraction of hydrogen from methane and that ethane is formed through the coupling of methyl intermediate. (author)

Kiss-induced severe anaphylactic reactions

Directory of Open Access Journals (Sweden)

Atanasković-Marković Marina

2010-01-01

Full Text Available Introduction. Ingestion is the principal route for food allergens to trigger allergic reaction in atopic persons. However, in some highly sensitive patients severe symptoms may develop upon skin contact and by inhalation. The clinical spectrum ranges from mild facial urticaria and angioedema to life-threatening anaphylactic reactions. Outline of Cases. We describe cases of severe anaphylactic reactions by skin contact, induced by kissing in five children with prior history of severe anaphylaxis caused by food ingestion. These cases were found to have the medical history of IgE mediated food allergy, a very high total and specific serum IgE level and very strong family history of allergy. Conclusion. The presence of tiny particles of food on the kisser's lips was sufficient to trigger an anaphylactic reaction in sensitized children with prior history of severe allergic reaction caused by ingestion of food. Allergic reaction provoked with food allergens by skin contact can be a risk factor for generalized reactions. Therefore, extreme care has to be taken in avoiding kissing allergic children after eating foods to which they are highly allergic. Considering that kissing can be a cause of severe danger for the food allergic patient, such persons should inform their partners about the risk factor for causing their food hypersensitivity.

Toehold-mediated strand displacement reaction triggered isothermal DNA amplification for highly sensitive and selective fluorescent detection of single-base mutation.

Science.gov (United States)

Zhu, Jing; Ding, Yongshun; Liu, Xingti; Wang, Lei; Jiang, Wei

2014-09-15

Highly sensitive and selective detection strategy for single-base mutations is essential for risk assessment of malignancy and disease prognosis. In this work, a fluorescent detection method for single-base mutation was proposed based on high selectivity of toehold-mediated strand displacement reaction (TSDR) and powerful signal amplification capability of isothermal DNA amplification. A discrimination probe was specially designed with a stem-loop structure and an overhanging toehold domain. Hybridization between the toehold domain and the perfect matched target initiated the TSDR along with the unfolding of the discrimination probe. Subsequently, the target sequence acted as a primer to initiate the polymerization and nicking reactions, which released a great abundant of short sequences. Finally, the released strands were annealed with the reporter probe, launching another polymerization and nicking reaction to produce lots of G-quadruplex DNA, which could bind the N-methyl mesoporphyrin IX to yield an enhanced fluorescence response. However, when there was even a single base mismatch in the target DNA, the TSDR was suppressed and so subsequent isothermal DNA amplification and fluorescence response process could not occur. The proposed approach has been successfully implemented for the identification of the single-base mutant sequences in the human KRAS gene with a detection limit of 1.8 pM. Furthermore, a recovery of 90% was obtained when detecting the target sequence in spiked HeLa cells lysate, demonstrating the feasibility of this detection strategy for single-base mutations in biological samples. Copyright © 2014 Elsevier B.V. All rights reserved.

Optimal conditions to use Pfu exo(-) DNA polymerase for highly efficient ligation-mediated polymerase chain reaction protocols.

Science.gov (United States)

Angers, M; Cloutier, J F; Castonguay, A; Drouin, R

2001-08-15

Ligation-Mediated Polymerase Chain Reaction (LMPCR) is the most sensitive sequencing technique available to map single-stranded DNA breaks at the nucleotide level of resolution using genomic DNA. LMPCR has been adapted to map DNA damage and reveal DNA-protein interactions inside living cells. However, the sequence context (GC content), the global break frequency and the current combination of DNA polymerases used in LMPCR affect the quality of the results. In this study, we developed and optimized an LMPCR protocol adapted for Pyrococcus furiosus exo(-) DNA polymerase (Pfu exo(-)). The relative efficiency of Pfu exo(-) was compared to T7-modified DNA polymerase (Sequenase 2.0) at the primer extension step and to Thermus aquaticus DNA polymerase (Taq) at the PCR amplification step of LMPCR. At all break frequencies tested, Pfu exo(-) proved to be more efficient than Sequenase 2.0. During both primer extension and PCR amplification steps, the ratio of DNA molecules per unit of DNA polymerase was the main determinant of the efficiency of Pfu exo(-), while the efficiency of Taq was less affected by this ratio. Substitution of NaCl for KCl in the PCR reaction buffer of Taq strikingly improved the efficiency of the DNA polymerase. Pfu exo(-) was clearly more efficient than Taq to specifically amplify extremely GC-rich genomic DNA sequences. Our results show that a combination of Pfu exo(-) at the primer extension step and Taq at the PCR amplification step is ideal for in vivo DNA analysis and DNA damage mapping using LMPCR.

Singlet versus Triplet Excited State Mediated Photoinduced Dehalogenation Reactions of Itraconazole in Acetonitrile and Aqueous Solutions.

Science.gov (United States)

Zhu, Ruixue; Li, Ming-de; Du, Lili; Phillips, David Lee

2017-04-06

Photoinduced dehalogenation of the antifungal drug itraconazole (ITR) in acetonitrile (ACN) and ACN/water mixed solutions was investigated using femtosecond and nanosecond time-resolved transient absorption (fs-TA and ns-TA, respectively) and nanosecond time-resolved resonance Raman spectroscopy (ns-TR 3 ) experiments. An excited resonance energy transfer is found to take place from the 4-phenyl-4,5-dihydro-3H-1,2,4-triazol-3-one part of the molecule to the 1,3-dichlorobenzene part of the molecule when ITR is excited by ultraviolet light. This photoexcitation is followed by a fast carbon-halogen bond cleavage that leads to the generation of radical intermediates via either triplet and/or singlet excited states. It is found that the singlet excited state-mediated carbon-halogen cleavage is the predominant dehalogenation process in ACN solvent, whereas a triplet state-mediated carbon-halogen cleavage prefers to occur in the ACN/water mixed solutions. The singlet-to-triplet energy gap is decreased in the ACN/water mixed solvents and this helps facilitate an intersystem crossing process, and thus, the carbon-halogen bond cleavage happens mostly through an excited triplet state in the aqueous solutions examined. The ns-TA and ns-TR 3 results also provide some evidence that radical intermediates are generated through a homolytic carbon-halogen bond cleavage via predominantly the singlet excited state pathway in ACN but via mainly the triplet state pathway in the aqueous solutions. In strong acidic solutions, protonation at the oxygen and/or nitrogen atoms of the 1,2,4-triazole-3-one group appears to hinder the dehalogenation reactions. This may offer the possibility that the phototoxicity of ITR due to the generation of aryl or halogen radicals can be reduced by protonation of certain moieties in suitably designed ITR halogen-containing derivatives.

Tin-free enantioselective radical reactions using silanes.

Science.gov (United States)

Sibi, Mukund P; Yang, Yong-Hua; Lee, Sunggi

2008-12-04

Readily available hexyl silane is an excellent choice as a H-atom donor and a chain carrier in Lewis acid mediated enantioselective radical reactions. Conjugate radical additions to alpha,beta-unsaturated imides at room temperature proceed in good yields and excellent enantioselectivities.

Characterization of Vancomycin Reactions and Linezolid Utilization in the Pediatric Population.

Science.gov (United States)

Lin, Samantha K; Mulieri, Kevin M; Ishmael, Faoud T

Red man syndrome (RMS) occurs because of non-IgE-mediated histamine release. Unlike vancomycin allergy, which necessitates the use of an alternative drug (often linezolid), RMS does not typically preclude further vancomycin use. Care should be taken to differentiate these reaction types from one another to prevent unnecessary vancomycin avoidance. To characterize vancomycin reaction types in our population, and to determine whether having a reaction consistent with RMS is associated with otherwise unexplained vancomycin avoidance and linezolid use. We retrospectively reviewed charts for children with documented vancomycin reactions. We classified the in-hospital reactions via an objective analysis and estimated the prevalence of different reaction types. We then identified children who received linezolid over 3 years, and investigated reasons for linezolid use instead of vancomycin. Of the 78 in-hospital reactions we characterized, 72 (92%) were objectively consistent with RMS, 5 we could not objectively classify (2 most likely RMS, 3 more suspicious for possible IgE-mediated allergy), and 1 was a non-RMS/non-IgE reaction. Of 60 children who received linezolid, 19 had previous reactions consistent with RMS, which should not preclude further vancomycin. Nevertheless, only 7 of 19 (37%) had a clear explanation for receiving linezolid instead of vancomycin compared with 32 of 39 (82%) children without previous vancomycin reactions (P linezolid utilization. We propose that this may be related to how reactions appear in the electronic medical record. Copyright © 2017 American Academy of Allergy, Asthma & Immunology. Published by Elsevier Inc. All rights reserved.

Manipulating radicals: Using cobalt to steer radical reactions

OpenAIRE

Chirilă, A.

2017-01-01

This thesis describes research aimed at understanding and exploiting metallo-radical reactivity and explores reactions mediated by square planar, low-spin cobalt(II) complexes. A primary goal was to uncover novel reactivity of discrete cobalt(III)-bound carbene radicals generated upon reaction of the cobalt(II) catalysts with carbene precursors. Another important goal was to replace cobalt(II)-porphyrin catalysts with cheaper and easier to prepare metallo-radical analogues. Therefore the cata...

Retrospective evaluation of bone pain palliation after samarium-153-EDTMP therapy Avaliação retrospectiva do tratamento da dor óssea metastática com Samário-153-EDTMP

Directory of Open Access Journals (Sweden)

Marcelo Tatit Sapienza

2004-01-01

Full Text Available PURPOSE: The aim of this study was to evaluate the degree of metastatic bone pain palliation and medullar toxicity associated with samarium-153-EDTMP treatment. METHODS: Seventy-three patients with metastatic bone pain having previously undergone therapy with samarium-153-EDTMP (1 mCi/kg were retrospectively evaluated. Routine follow-up included pain evaluation and blood counts for 2 months after treatment. Pain was evaluated using a subjective scale (from 0 to 10 before and for 8 weeks after the treatment. Blood counts were obtained before treatment and once a week for 2 months during follow-up. Dosimetry, based upon the urinary excretion of the isotope, was estimated in 41 individuals, and the resulting radiation absorbed doses were correlated with hematological data. RESULTS: Reduction in pain scores of 75% to 100% was obtained in 36 patients (49%, with a decrease of 50% to 75%, 25% to 50%, and 0% to 25% in, respectively, 20 (27%, 10 (14%, and 7 (10% patients. There was no significant relationship between the pain response and location of the primary tumor (breast or prostate cancer. Mild to moderate myelosuppression was noted in 75.3% of patients, usually with hematological recovery at 8 weeks. The mean bone marrow dose was 347 ± 65 cGy, and only a weak correlation was found between absorbed dose and myelosuppression (Pearson coefficient = .4. CONCLUSIONS: Samarium-153-EDTMP is a valuable method for metastatic bone pain palliation. A mild to moderate and transitory myelosuppression is the main toxicity observed after samarium therapy, showing a weak correlation with dosimetric measures.OBJETIVO: O presente trabalho teve por objetivo avaliar o efeito paliativo da dor e a toxicidade medular associados ao tratamento com Samário-153-EDTMP em pacientes com metástases ósseas. MÉTODOS: O estudo foi realizado de forma retrospectiva, a partir do levantamento de prontuário de 178 pacientes submetidos a tratamento com 1mCi/kg de 153Sm

Allergen immunotherapy for IgE-mediated food allergy

DEFF Research Database (Denmark)

Nurmatov, Ulugbek; Dhami, S; Arasi, S.

2017-01-01

Background: The European Academy of Allergy and Clinical Immunology (EAACI) is developing Guidelines for Allergen Immunotherapy (AIT) for IgE-mediated Food Allergy. To inform the development of clinical recommendations, we sought to critically assess evidence on the effectiveness, safety and cost-effectiveness...... economic analyses. Conclusions: AIT may be effective in raising the threshold of reactivity to a range of foods in children with IgE-mediated food allergy whilst receiving (i.e. desensitization) and post-discontinuation of AIT. It is, however, associated with a modest increased risk in serious systemic...... adverse reactions and a substantial increase in minor local adverse reactions. More data are needed in relation to adults, long term effects, the impact on QoL and the cost-effectiveness of AIT....

Synthesis of Pyrroloquinones via a CAN Mediated Oxidative Free Radical Reaction of 1,3-Dicarbonyl Compounds with Aminoquinones

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Thao Nguyen

2013-01-01

Full Text Available Pyrroloquinone ring systems are important structural units present in many biologically active molecules including a number of marine alkaloids. For example, they are found in a series of marine metabolites, such as tsitsikammamines, zyzzyanones, wakayin, and terreusinone. Several of these alkaloids have exhibited antimicrobial, antimalarial, antifungal, antitumor, and photoprotecting activities. Synthesis of pyrroloquinone unit is the key step in the synthesis of many of these important organic molecules. Here, we present a ceric (IV ammonium nitrate (CAN mediated oxidative free radical cyclization reaction of 1,3-dicarbonyl compounds with aminoquinones as a facile methodology for making various substituted pyrroloquinones. 1,3-dicarbonyl compounds used in this study are ethyl acetoacetate, acetylacetone, benzoyl acetone, and N,N-dimethyl acetoacetamide. The aminoquinones used in this study are 2-(benzylaminonaphthalene-1,4-dione and 6-(benzylamino-1-tosyl-1H-indole-4,7-dione. The yields of the synthesized pyrroloquinones ranged from 23–91%.

Preparation and dosimetry of radiotherapeutic particles for arthropaties; Preparacion y dosimetria de particulas radioterapeuticas para artropatias

Energy Technology Data Exchange (ETDEWEB)

Gonzalez Z, M A [Departamento de Medicina Nuclear, Instituto Nacional de Pediatria (Mexico); Ferro F, G [Departamento de Materiales Radiactivos, Instituto nacional de Investigaciones Nucleares, Salazar, Estado de Mexico C.P. 52045 (Mexico); Rivera M, T; Azorin N, J [Departamento de Fisica, UAM Iztapalapa, Mexico D.F. (Mexico)

1999-07-01

It was developed a new formulation of macro aggregates of Samarium 153 ({sup 153} Sm-MH) for the arthropaties treatment. The radio pharmaceutic was prepared by reaction of Samarium 153 chloride (SmCl{sub 3}) in aqueous environment with sodium boron hydride in NaOH 0.5 N. The microscopic analysis shown that the particles have an average size of 4% m (range 1-14 {mu} m). The velocity of sedimentation was 0.008 cm/min with high stability in vitro in human serum. The biological studies in healthy rabbits, shown that the complex is retained inside the articulation still eight days after of the administration of the radiopharmaceutical. Likewise, it is presented the data of absorbed dose in the different target organs, which was determined by thermoluminescent dosimetry (TLD) through the use of a REMCAL phantom (radiation equivalent manikin calibration). (Author)

Preparation and dosimetry of radiotherapeutic particles for arthropaties

International Nuclear Information System (INIS)

Gonzalez Z, M.A.; Ferro F, G.; Rivera M, T.; Azorin N, J.

1999-01-01

It was developed a new formulation of macro aggregates of Samarium 153 ( 153 Sm-MH) for the arthropaties treatment. The radio pharmaceutic was prepared by reaction of Samarium 153 chloride (SmCl 3 ) in aqueous environment with sodium boron hydride in NaOH 0.5 N. The microscopic analysis shown that the particles have an average size of 4% m (range 1-14 μ m). The velocity of sedimentation was 0.008 cm/min with high stability in vitro in human serum. The biological studies in healthy rabbits, shown that the complex is retained inside the articulation still eight days after of the administration of the radiopharmaceutical. Likewise, it is presented the data of absorbed dose in the different target organs, which was determined by thermoluminescent dosimetry (TLD) through the use of a REMCAL phantom (radiation equivalent manikin calibration). (Author)

Effects of samarium (Sm) additions on the microstructure and mechanical properties of as-cast and hot-extruded Mg-5 wt%Al-3 wt%Ca-based alloys

International Nuclear Information System (INIS)

Son, Hyeon-Taek; Lee, Jae-Seol; Kim, Dae-Guen; Yoshimi, Kyosuke; Maruyama, Kouichi

2009-01-01

Samarium (Sm) additions to as-cast Mg-5Al-3Ca-based alloys result in changes, such as equiaxed grains and a refined grain size. The microstructure of as-cast Mg-5Al-3Ca-xSm alloys consists of an α-Mg matrix, a (Mg, Al) 2 Ca eutectic phase, and an Al 2 Sm intermetallic compound. In as-cast alloys, the (Mg, Al) 2 Ca eutectic phase was located at grain boundaries with a chain structure, and the Al 2 Sm intermetallic compounds were homogeneously distributed at the α-Mg matrix and grain boundaries. The eutectic phase of the extruded alloys was elongated in the extrusion direction and crushed into fine particles because of severe deformation during hot extrusion, and the grain size was refined with an increased amount of Sm addition. The maximum values of the yield strength and tensile strength were 313 MPa and 330 MPa at 2 wt%Sm alloy content, respectively

AAPH-mediated antioxidant reactions of secoisolariciresinol and SDG.

Science.gov (United States)

Hosseinian, Farah S; Muir, Alister D; Westcott, Neil D; Krol, Ed S

2007-02-21

Secoisolariciresinol (SECO ) is the major lignan found in flaxseed (Linum usitatissimum L.) and is present in a polymer that contains secoisolariciresinol diglucoside (SDG ). SECO, SDG and the polymer are known to have a number of health benefits, including reduction of serum cholesterol levels, delay in the onset of type II diabetes and decreased formation of breast, prostate and colon cancers. The health benefits of SECO and SDG may be partially attributed to their antioxidant properties. To better understand their antioxidant properties, SECO and SDG were oxidized using 2,2'-azobis(2-amidinopropane), an in vitro model of radical scavenging. The major lignan radical-scavenging oxidation products and their formation over time were determined. SDG was converted to four major products, which were the result of a phenoxyl radical intermediate. One of these products, a dimer of SDG, decomposed under the reaction conditions to form two of the other major products, and . SECO was converted to five major products, two of which were also the result of a phenoxyl radical intermediate. The remaining products were the result of an unexpected alkoxyl radical intermediate. The phenol oxidation products were stable under the reaction conditions, whereas two of the alcohol oxidation products decomposed. In general, only one phenol group on the lignans was oxidized, suggesting that the number of phenols per molecule may not predict radical scavenging antioxidant ability of lignans. Finally, SECO is a superior antioxidant to SDG, and it may be that the additional alcohol oxidation pathway contributes to its greater antioxidant ability.

Hypersensitivity reactions in patients receiving hemodialysis.

Science.gov (United States)

Butani, Lavjay; Calogiuri, Gianfranco

2017-06-01

To describe hypersensitivity reactions in patients receiving maintenance hemodialysis. PubMed search of articles published during the past 30 years with an emphasis on publications in the past decade. Case reports and review articles describing hypersensitivity reactions in the context of hemodialysis. Pharmacologic agents are the most common identifiable cause of hypersensitivity reactions in patients receiving hemodialysis. These include iron, erythropoietin, and heparin, which can cause anaphylactic or pseudoallergic reactions, and topical antibiotics and anesthetics, which lead to delayed-type hypersensitivity reactions. Many hypersensitivity reactions are triggered by complement activation and increased bradykinin resulting from contact system activation, especially in the context of angiotensin-converting enzyme inhibitor use. Several alternative pharmacologic preparations and dialyzer membranes are available, such that once an etiology for the reaction is established, recurrences can be prevented without affecting the quality of care provided to patients. Although hypersensitivity reactions are uncommon in patients receiving hemodialysis, they can be life-threatening. Moreover, considering the large prevalence of the end-stage renal disease population, the implications of such reactions are enormous. Most reactions are pseudoallergic and not mediated by immunoglobulin E. The multiplicity of potential exposures and the complexity of the environment to which patients on dialysis are exposed make it challenging to identify the precise cause of these reactions. Great diligence is needed to investigate hypersensitivity reactions to avoid recurrence in this high-risk population. Copyright © 2017 American College of Allergy, Asthma & Immunology. Published by Elsevier Inc. All rights reserved.

Effect of glucocorticosteroid treatment on ovalbumin-induced IgE-mediated immediate and late allergic response in guinea pig.

Science.gov (United States)

Andersson, P; Brange, C; von Kogerer, B; Sonmark, B; Stahre, G

1988-01-01

The effect of glucocorticosteroid (GCS) treatment on ovalbumine-induced IgE-mediated immediate and late allergic response was studied in sensitized guinea pigs. The results show that the GCS budesonide (BUD) inhibits the allergen-induced IgE-mediated immediate and late bronchial obstruction. The effect on the early reaction is correlated to the inhibition of leukotrienes and histamine release. The importance of mediator release inhibition for the antianaphylactic effect of GCS is discussed. In examining the effect on the late reaction, it was found that BUD had to be present during the early reaction but did not inhibit the early reaction. Furthermore, the effect on the late reaction was correlated to the inhibition of vascular leakage but not to the infiltration of inflammatory cells as examined in bronchoalveolar lavage. The results indicate that some triggering factors important for the development of the late reaction are released during the early reaction. Inhibition of the release of that factor or the activation of inflammatory cells by that factor might be the mechanism behind the antiinflammatory activities of GCS.

Molecular Controls of the Oxygenation and Redox Reactions of Hemoglobin

Science.gov (United States)

Henkens, Robert; Alayash, Abdu I.; Banerjee, Sambuddha; Crumbliss, Alvin L.

2013-01-01

Abstract Significance: The broad classes of O2-binding proteins known as hemoglobins (Hbs) carry out oxygenation and redox functions that allow organisms with significantly different physiological demands to exist in a wide range of environments. This is aided by allosteric controls that modulate the protein's redox reactions as well as its O2-binding functions. Recent Advances: The controls of Hb's redox reactions can differ appreciably from the molecular controls for Hb oxygenation and come into play in elegant mechanisms for dealing with nitrosative stress, in the malarial resistance conferred by sickle cell Hb, and in the as-yet unsuccessful designs for safe and effective blood substitutes. Critical Issues: An important basic principle in consideration of Hb's redox reactions is the distinction between kinetic and thermodynamic reaction control. Clarification of these modes of control is critical to gaining an increased understanding of Hb-mediated oxidative processes and oxidative toxicity in vivo. Future Directions: This review addresses emerging concepts and some unresolved questions regarding the interplay between the oxygenation and oxidation reactions of structurally diverse Hbs, both within red blood cells and under acellular conditions. Developing methods that control Hb-mediated oxidative toxicity will be critical to the future development of Hb-based blood substitutes. Antioxid. Redox Signal. 18, 2298–2313. PMID:23198874

Parenting Stress, Parental Reactions, and Externalizing Behavior From Ages 4 to 10.

Science.gov (United States)

Mackler, Jennifer S; Kelleher, Rachael T; Shanahan, Lilly; Calkins, Susan D; Keane, Susan P; O'Brien, Marion

2015-04-01

The association between parenting stress and child externalizing behavior, and the mediating role of parenting, has yielded inconsistent findings; however, the literature has typically been cross-sectional and unidirectional. In the current study the authors examined the longitudinal transactions among parenting stress, perceived negative parental reactions, and child externalizing at 4, 5, 7, and 10 years old. Models examining parent effects (parenting stress to child behavior), child effects (externalizing to parental reactions and stress), indirect effects of parental reactions, and the transactional associations among all variables, were compared. The transactional model best fit the data, and longitudinal reciprocal effects emerged between parenting stress and externalizing behavior. The mediating role of parental reactions was not supported; however, indirect effects suggest that parenting stress both is affected by and affects parent and child behavior. The complex associations among parent and child variables indicate the importance of interventions to improve the parent-child relationship and reducing parenting stress.

Method of making ionic liquid mediated sol-gel sorbents

Science.gov (United States)

Malik, Abdul; Shearrow, Anne M.

2017-01-31

Ionic liquid (IL)-mediated sol-gel hybrid organic-inorganic materials present enormous potential for effective use in analytical microextraction. One obstacle to materializing this prospect arises from high viscosity of ILs significantly slowing down sol-gel reactions. A method was developed which provides phosphonium-based, pyridinium-based, and imidazolium-based IL-mediated advanced sol-gel organic-inorganic hybrid materials for capillary microextraction. Scanning electron microscopy results demonstrate that ILs can serve as porogenic agents in sol-gel reactions. IL-mediated sol-gel coatings prepared with silanol-terminated polymers provided up to 28 times higher extractions compared to analogous sol-gel coatings prepared without any IL in the sol solution. This study shows that IL-generated porous morphology alone is not enough to provide effective extraction media: careful choice of the organic polymer and the precursor with close sol-gel reactivity must be made to ensure effective chemical bonding of the organic polymer to the created sol-gel material to be able to provide the desired sorbent characteristics.

Degradation of anthracene by laccase of Trametes versicolor in the presence of different mediator compounds.

Science.gov (United States)

Johannes, C; Majcherczyk, A; Hüttermann, A

1996-10-01

Laccase of Trametes versicolor was generally able to oxidize anthracene in vitro. After 72 h incubation about 35% of the anthracene was transformed stoichiometrically to 9,10-anthraquinone. Transformation of anthracene increased rapidly in the presence of different mediators that readily generate stable radicals: 2,2'-azino-bis-(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS) and 1-hydroxybenzotriazole. For the reaction, the presence of both the laccase and the mediator was necessary. In the presence of 0.005 mM 1-hydroxybenzotriazole this conversion had removed 47% of the anthracene after 72 h; 75% of the substrate was oxidized during this period when ABTS (1 mM) was used as mediator. In contrast to reactions without or with only low concentrations of a mediator, there was a discrepancy between the disappearance of anthracene and the formation of 9,10-anthraquinone in mediator-forced reactions. Coupling-products of mediators with anthracene degradation products were found. Anthracene disappeared nearly completely after incubation for 72 h with laccase in a 0.1 mM solution of 1-hydroxybenzotriazole and was transformed to 9,10-anthraquinone in about 80% yield; 90% of the substrate was transformed in the presence of ABTS (2.0 mM) resulting again in 80% quinone. Phenothiazine was not effective in this system.

IgE-mediated hypersensitivity reactions to cannabis in laboratory personnel.

Science.gov (United States)

Herzinger, T; Schöpf, P; Przybilla, B; Ruëff, F

2011-01-01

There have been sporadic reports of hypersensitivity reactions to plants of the Cannabinaceae family (hemp and hops), but it has remained unclear whether these reactions are immunologic or nonimmunologic in nature. We examined the IgE-binding and histamine-releasing properties of hashish and marijuana extracts by CAP-FEIA and a basophil histamine release test. Two workers at a forensic laboratory suffered from nasal congestion, rhinitis, sneezing and asthmatic symptoms upon occupational contact with hashish or marijuana, which they had handled frequently for 25 and 16 years, respectively. Neither patient had a history of atopic disease. Serum was analyzed for specific IgE antibodies to hashish or marijuana extract by research prototype ImmunoCAP, and histamine release from basophils upon exposure to hashish or marijuana extracts was assessed. Results were matched to those of 4 nonatopic and 10 atopic control subjects with no known history of recreational or occupational exposure to marijuana or hashish. Patient 1 had specific IgE to both hashish and marijuana (CAP class 2), and patient 2 to marijuana only (CAP class 2). Controls proved negative for specific IgE except for 2 atopic individuals with CAP class 1 to marijuana and 1 other atopic individual with CAP class 1 to hashish. Stimulation of basophils with hashish or marijuana extracts elicited histamine release from basophils of both patients and 4 atopic control subjects. Our results suggest an IgE-related pathomechanism for hypersensitivity reactions to marijuana or hashish. Copyright © 2011 S. Karger AG, Basel.

Exciplex mediated photoinduced electron transfer reactions of phthalocyanine-fullerene dyads

NARCIS (Netherlands)

Niemi, Marja; Tkachenko, Nikolai V.; Efimov, Alexander; Lehtivuori, Heli; Ohkubo, Kei; Fukuzumi, Shunichi; Lemmetyinen, Helge

2008-01-01

Evidences of an intramolecular exciplex intermediate in a photoinduced electron transfer (ET) reaction of double-linked free-base and zinc phthalocyanine-C-60 dyads were found. This was the first time for a dyad with phthalocyanine donor. Excitation of the phthalocyanine moiety of the dyads results

Glutaredoxin-2 is required to control oxidative phosphorylation in cardiac muscle by mediating deglutathionylation reactions.

Science.gov (United States)

Mailloux, Ryan J; Xuan, Jian Ying; McBride, Skye; Maharsy, Wael; Thorn, Stephanie; Holterman, Chet E; Kennedy, Christopher R J; Rippstein, Peter; deKemp, Robert; da Silva, Jean; Nemer, Mona; Lou, Marjorie; Harper, Mary-Ellen

2014-05-23

Glutaredoxin-2 (Grx2) modulates the activity of several mitochondrial proteins in cardiac tissue by catalyzing deglutathionylation reactions. However, it remains uncertain whether Grx2 is required to control mitochondrial ATP output in heart. Here, we report that Grx2 plays a vital role modulating mitochondrial energetics and heart physiology by mediating the deglutathionylation of mitochondrial proteins. Deletion of Grx2 (Grx2(-/-)) decreased ATP production by complex I-linked substrates to half that in wild type (WT) mitochondria. Decreased respiration was associated with increased complex I glutathionylation diminishing its activity. Tissue glucose uptake was concomitantly increased. Mitochondrial ATP output and complex I activity could be recovered by restoring the redox environment to that favoring the deglutathionylated states of proteins. Grx2(-/-) hearts also developed left ventricular hypertrophy and fibrosis, and mice became hypertensive. Mitochondrial energetics from Grx2 heterozygotes (Grx2(+/-)) were also dysfunctional, and hearts were hypertrophic. Intriguingly, Grx2(+/-) mice were far less hypertensive than Grx2(-/-) mice. Thus, Grx2 plays a vital role in modulating mitochondrial metabolism in cardiac muscle, and Grx2 deficiency leads to pathology. As mitochondrial ATP production was restored by the addition of reductants, these findings may be relevant to novel redox-related therapies in cardiac disease. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Exploration of new tritium labelling methods

International Nuclear Information System (INIS)

Andres, H.; Jaiswal, D.K.; Morimoto, H.; Saljoughian, M.; Than, C.; Willimas, P.G.; Zippi, E.M.

1997-01-01

Full text: A great deal of elegant chemistry is available for hydride transfer reactions, and could be adapted for tritium labelling. Nevertheless, most high level tritiation reactions still involve either hydrogenation (alkene or alkyne precursor) or catalytic dehalogenation. In the last decade we have endeavored to propose and popularize alternative labelling techniques and reagents, including: i) the synthesis of new precursors for the production of methyl iodide; ii) the synthesis of methylene diiodide; iii) the production and use of T 2 O, and solvents made from it, eg. CH 3 COOT, CF 3 COOT; iv) high specific activity hydride reagents, eg. LiAIT 4 , LiEt 3 BT; (Bu n ) 3 SnT, ZrCp 2 CIT, LiT, Li(OCH 3 ) 3 BT, Ph 2 SiT 2 , BT 3 -THF, Li/Na/KBT 4 ; v) reduction with diimide; vi) use of T 2 O in special reactions such as the Shapiro reaction and Brook rearrangement; and vii) developments of a new acetylation reagent. We have also initiated and continued a number of innovative applications of tritium NMR spectroscopy. Many of these projects have grown out of User or Collaborator requirements at the NTLF. We regard this stimulus to develop and refine both tritiation and NMR techniques as healthy and challenging

A mathematical analysis of Prx2-STAT3 disulfide exchange rate constants for a bimolecular reaction mechanism.

Science.gov (United States)

Langford, Troy F; Deen, William M; Sikes, Hadley D

2018-03-22

Appreciation of peroxiredoxins as the major regulators of H 2 O 2 concentrations in human cells has led to a new understanding of redox signaling. In addition to their status as the primary reducers of H 2 O 2 to water, the oxidized peroxiredoxin byproduct of this reaction has recently been shown capable of participation in H 2 O 2 -mediated signaling pathways through disulfide exchange reactions with the transcription factor STAT3. The dynamics of peroxidase-transcription factor disulfide exchange reactions have not yet been considered in detail with respect to how these reactions fit into the larger network of competing reactions in human cells. In this study, we used a kinetic model of oxidation and reduction reactions related to H 2 O 2 metabolism in the cytosol of human cells to study the dynamics of peroxiredoxin-2 mediated oxidation of the redox-regulated transcription factor STAT3. In combination with previously reported experimental data, the model was used to estimate the rate coefficient of a biomolecular reaction between Prx2 and STAT3 for two sets of assumptions that constitute lower and upper bound cases. Using these estimates, we calculated the relative rates of the reaction of oxidized peroxiredoxin-2 and STAT3 and other competing reactions in the cytosol. These calculations revealed that peroxiredoxin-2-mediated oxidation of STAT3 likely occurs at a much slower rate than competing reactions in the cytosol. This analysis suggests the existence of more complex mechanisms, potentially involving currently unknown protein-protein recognition partners, which facilitate disulfide exchange reactions between peroxiredoxin-2 and STAT3. Copyright © 2018 Elsevier Inc. All rights reserved.

Adaptive and innate immune reactions regulating mast cell activation: from receptor-mediated signaling to responses

DEFF Research Database (Denmark)

Tkaczyk, Christine; Jensen, Bettina M; Iwaki, Shoko

2006-01-01

differentially activate multiple signaling pathways within the mast cells required for the generation and/or release of inflammatory mediators. Thus, the composition of the suite of mediators released and the physiologic ramifications of these responses are dependent on the stimuli and the microenvironment...

Carbohydrate carbocyclization by a zinc-mediated tandem reaction and ring-closing enyne metathesis

DEFF Research Database (Denmark)

Poulsen, Carina Storm; Madsen, Robert

2002-01-01

reaction, an amino group can be introduced in the 1,7-enyne products. Addition of 2-TMS-ethynylcerium(III) chloride after the reductive ring-opening produces the corresponding 1,6-enynes. Further annulation of the product 1,3-dienes can be achieved through a Diels-Alder reaction with good control of stereo...

Perceived Insider Status and Feedback Reactions: A Dual Path of Feedback Motivation Attribution

Directory of Open Access Journals (Sweden)

Weijiong Wu

2017-05-01

Full Text Available Many studies have evaluated how the characteristics of feedback receiver, feedback deliverer and feedback information influence psychological feedback reactions of the feedback receiver while largely neglecting that feedback intervention is a kind of social interaction process. To address this issue, this study proposes that employees’ perceived insider status (PIS, as a kind of employee-organization relationship, could also influence employees’ reactions to supervisory feedback. In particular, this study investigates the influence of PIS focusing on affective and cognitive feedback reactions, namely feedback satisfaction and feedback utility. Surveys were conducted in a machinery manufacturing company in the Guangdong province of China. Samples were collected from 192 employees. Data analysis demonstrated that PIS and feedback utility possessed a U-shaped relationship, whereas PIS and feedback satisfaction exhibited positively linear relationships. The analysis identified two kinds of mediating mechanisms related to feedback satisfaction and feedback utility. Internal feedback motivation attribution partially mediated the relationship between PIS and feedback satisfaction but failed to do the same with respect to the relationship between PIS and feedback utility. In contrast, external feedback motivation attribution partially mediated the relationship between PIS and feedback utility while failing to mediate the relationship between PIS and feedback satisfaction. Theoretical contributions and practical implications of the findings are discussed at the end of the paper.

The mediation reaction between the external couple Ferri/Ferrocyanide and Os(II) bipyridile poly-vinylpyridile films coated onto glassy carbon electrodes

Energy Technology Data Exchange (ETDEWEB)

Ybarra, Gabriel; Moina, Carlos [Centro de Investigacion sobre Electrodeposicion y Procesos Superficiales, Instituto Nacional de Tecnologia Industrial, CC 157, 1650 San Martin (Argentina); Florit, M. Ines [INIFTA, Facultad de Ciencias Exactas, UNLP, Suc. 4, CC 16, 1900 La Plata (Argentina); Posadas, Dionisio [INIFTA, Facultad de Ciencias Exactas, UNLP, Suc. 4, CC 16, 1900 La Plata (Argentina)], E-mail: dposadas@inifta.unlp.edu.ar

2008-05-30

The oxidation-reduction of the Ferri/Ferrocyanide couple in solution onto modified glassy carbon Rotating Disk Electrodes (RDE) covered by Os(II) bipyridile poly-vinylpyridile (OsBPP) polymer was studied at room temperature. Steady state polarization curves were carried out as a function of the rotation speed, the polymer thickness and the concentration of redox centers within the polymer. This system has the characteristic that the formal redox potentials of both the external redox couple (E{sup 0}'(Fe(CN){sub 6}{sup 3-/4-}) = + 0.225 V vs. SCE) and the mediator polymer (E{sup 0}'(OsBPP) = 0.260 V vs. SCE) lie very close. It is demonstrated that diffusion of the Ferri/Ferrocyanide inside the polymer can be ruled out. Since the processes of charge transfer at the metal/polymer and the mediating reaction are fast, the experimental results can be interpreted in terms of a kinetics in which the charge transport in the polymer or the diffusion in the solution may be the rate determining step, according to the experimental conditions. A simple model is considered that allows interpreting the experimental results quantitatively. Application of this model allows the determination of the diffusion coefficient of the electrons within the film, D{sub e} {approx} 10{sup -10} cm{sup 2} s{sup -1}.

Pharmacokinetics of labelled compounds with technetium-99m and samarium-153; Farmacocinetica de compuestos marcados con tecnecio-99m y samario-153

Energy Technology Data Exchange (ETDEWEB)

Borda O, L B; Torres L, M N

1997-07-01

The purpose of this investigation was to establish the different pharmacokinetics parameters of the main radiopharmaceuticals labeled with technetium-99m and samarium-153. These parameters could be subsequently used as reference to compare other products with the same use. Mathematical models and a computerized pharmacokinetic program were used to this purpose. A biodistribution study in quadruplicate and/or quintuplicate was conducted for each radiopharmaceutical, data was was obtained in injection dose percentages. The biodistribution study involved the injection of a predetermined dose of the radiopharmaceutical into animals (rats or mice), which were subsequently put away at different time intervals, removing the relevant organs. Activity in each organ was read by means of a well-type NaI scintillation counter, data obtained in activity counts was transformed into injection dose percentages. Based on these percentages, the mathematical model was constructed and the pharmacokinetic parameters were obtained using the computerized program Expo 2 v. 1, which is written in C language and works in windows. Analyzing the results obtained, we can conclude that the use of the Expo 2 v. 1 program for a bi compartmental analysis allowed us to obtain reliable pharmacokinetic parameters which describe what happens in the organism when the radiopharmaceutical passes from the central compartment to the peripheral one and vice versa.

Role of mobile passenger lymphocytes in the rejection of renal and cardiac allografts in the rat. A passenger lymphocyte-mediated graft-versus-host reaction amplifies the host response

International Nuclear Information System (INIS)

van Vrieshilfgaarde, R.; Hermans, P.; Terpstra, J.L.; van Breda Viresman, P.J.

1980-01-01

It is demonstrated that passenger lymphocytes migrate out of rat renal allografts into host spleens in a radioresistant fashion. These mobile passenger lymphocytes within BN kidney and heart transplants are immunocompetent, since they elicit a graft-versus-host (GVH) reaction in the spleens of (LEW x BN)F2 hybrid hosts. The greater GVH reaction in (LEW x BN)F1 recipients of BN kidneys reflects the greater number of mobile passenger lymphocytes in the kidney when compared to the heart. The mobile passenger lymphocytes within BN renal allografts also cause a proliferative response in the spleens of the LEW hosts as well as an accelerated rejection of BN renal allografts when compared to BN cardiac allografts, for the differences between BN kidney and heart, both in terms of splenomegaly elicited in LEW as well as tempo of rejection, are abolished by total body x-irradiation of the donor with 900 rad. Results indicate that a mobile passenger lymphocyte mediated GVH reaction in the central lymphoid organs of the host augments the host response to allogenic kidneys and contributes materially to first-set renal allograft rejection; this GVH reaction on the other hand is not conspicuously present in LEW recipients of BN cardiac allografts and has therefore little effect on first-set cardiac allograft rejection

Prototype Willingness Model Drinking Cognitions Mediate Personalized Normative Feedback Efficacy.

Science.gov (United States)

Lewis, Melissa A; Litt, Dana M; Tomkins, Mary; Neighbors, Clayton

2017-05-01

Personalized normative feedback (PNF) interventions have been shown to be efficacious at reducing college student drinking. Because descriptive norms have been shown to mediate PNF efficacy, the current study focused on examining additional prototype willingness model social reaction cognitions, namely, prototypes and willingness, as mediators of intervention efficacy. We expected the PNF interventions to be associated with increased prototype favorability of students who do not drink, which would in turn be associated with decreased willingness to drink and subsequently, less drinking. The current study included 622 college students (53.2% women; 62% Caucasian) who reported one or more heavy drinking episodes in the past month and completed baseline and three-month follow-up assessments. As posited by the framework of the prototype willingness model, sequential mediation analyses were conducted to evaluate increases in abstainer prototype favorability on willingness on drinking, and subsequently willingness to drink on drinking behavior. Mediation results revealed significant indirect effects of PNF on three-month drinking through three-month prototypes and willingness, indicating that the social reaction pathway of the prototype willingness model was supported. Findings have important implications for PNF interventions aiming to reduce high-risk drinking among college students. Study findings suggest that we should consider looking at additional socially-based mediators of PNF efficacy in addition to perceived descriptive norms.

Versatile Dual Photoresponsive System for Precise Control of Chemical Reactions.

Science.gov (United States)

Xu, Can; Bing, Wei; Wang, Faming; Ren, Jinsong; Qu, Xiaogang

2017-08-22

A versatile method for photoregulation of chemical reactions was developed through a combination of near-infrared (NIR) and ultraviolet (UV) light sensitive materials. This regulatory effect was achieved through photoresponsive modulation of reaction temperature and pH values, two prominent factors influencing reaction kinetics. Photothermal nanomaterial graphene oxide (GO) and photobase reagent malachite green carbinol base (MGCB) were selected for temperature and pH regulation, respectively. Using nanocatalyst- and enzyme-mediated chemical reactions as model systems, we demonstrated the feasibility and high efficiency of this method. In addition, a photoresponsive, multifunctional "Band-aid"-like hydrogel platform was presented for programmable wound healing. Overall, this simple, efficient, and reversible system was found to be effective for controlling a wide variety of chemical reactions. Our work may provide a method for remote and sustainable control over chemical reactions for industrial and biomedical applications.

Identification of ochratoxin A producing Aspergillus carbonarius and A. niger clade isolated from grapes using the loop-mediated isothermal amplification (LAMP) reaction.

Science.gov (United States)

Storari, M; von Rohr, R; Pertot, I; Gessler, C; Broggini, G A L

2013-04-01

To develop two assays based on the loop-mediated isothermal amplification (LAMP) of DNA for the quick and specific identification of Aspergillus carbonarius and ochratoxigenic strains of the Aspergillus niger clade isolated from grapes. Two sets of primers were designed based on the polyketide synthase genes involved or putatively involved in ochratoxin A (OTA) biosynthesis in A. carbonarius and A. niger clade. Hydroxynaphthol blue was used as indirect method to indicate DNA amplification. The limit of detection of both assays was comparable to that of a PCR reaction. Specificities of the reactions were tested using DNA from different black aspergilli isolated from grapes. The two LAMP assays were then used to identify A. carbonarius and ochratoxigenic A. niger and A. awamori grown in pure cultures without a prior DNA extraction. The two LAMP assays permitted to quickly and specifically identify DNA from OTA-producing black aspergilli, as well as isolates grown in pure culture. Monitoring vineyards for the presence of OTA-producing strains is part of the measures to minimize the occurrence of OTA in grape products. The two LAMP assays developed here could be potentially used to speed the screening process of vineyards for the presence of OTA-producing black aspergilli. © 2013 The Society for Applied Microbiology.

Chemical reactions directed Peptide self-assembly.

Science.gov (United States)

Rasale, Dnyaneshwar B; Das, Apurba K

2015-05-13

Fabrication of self-assembled nanostructures is one of the important aspects in nanoscience and nanotechnology. The study of self-assembled soft materials remains an area of interest due to their potential applications in biomedicine. The versatile properties of soft materials can be tuned using a bottom up approach of small molecules. Peptide based self-assembly has significant impact in biology because of its unique features such as biocompatibility, straight peptide chain and the presence of different side chain functionality. These unique features explore peptides in various self-assembly process. In this review, we briefly introduce chemical reaction-mediated peptide self-assembly. Herein, we have emphasised enzymes, native chemical ligation and photochemical reactions in the exploration of peptide self-assembly.

Biochemistry and pathology of radical-mediated protein oxidation

DEFF Research Database (Denmark)

Dean, R T; Fu, S; Stocker, R

1997-01-01

Radical-mediated damage to proteins may be initiated by electron leakage, metal-ion-dependent reactions and autoxidation of lipids and sugars. The consequent protein oxidation is O2-dependent, and involves several propagating radicals, notably alkoxyl radicals. Its products include several catego...

Development of mediator-type biosensor to wirelessly monitor whole cholesterol concentration in fish.

Science.gov (United States)

Takase, Mai; Murata, Masataka; Hibi, Kyoko; Huifeng, Ren; Endo, Hideaki

2014-04-01

We developed a wireless monitoring system to monitor fish condition by tracking the change in whole cholesterol concentration. The whole cholesterol concentration of fish is a source of steroid hormones or indicator of immunity level, which makes its detection important for tracking physiological condition of fish. Wireless monitoring system comprises of mediator-type biosensor and wireless transmission device. Biosensor is implantable to fish body, and transmission device is so light, in that fish is allowed to swim freely during monitoring. Cholesterol esterase and oxidase were fixated on to the detection site of biosensor and used to detect the whole cholesterol concentration. However, cholesterol oxidase incorporates oxidation-reduction reaction of oxygen for detection, which concentration fluctuates easily due to change in environmental condition. Meanwhile, mediator-type biosensor enables monitoring of whole cholesterol concentration by using mediator to substitute that oxidation-reduction reaction of oxygen. Characteristic of fabricated mediator-type biosensor was tested. The sensor output current of mediator-type biosensor remained stable compared to output current of non-mediator-type biosensor under fluctuating oxygen concentration of 0-8 ppm, which implied that this sensor is less affected by change in dissolved oxygen concentration. That biosensor was then implanted into fish for wireless monitoring. As a result, approximately 48 h of real-time monitoring was successful.

Agrobacterium -induced hypersensitive necrotic reaction in plant cells

African Journals Online (AJOL)

High necrosis and poor survival rate of target plant tissues are some of the major factors that affect the efficiency of Agrobacterium-mediated T-DNA transfer into plant cells. These factors may be the result of, or linked to, hypersensitive defense reaction in plants to Agrobacterium infection, which may involve the recognition ...

Immunological Reaction in TNF-α-Mediated Osteoclast Formation and Bone Resorption In Vitro and In Vivo

Directory of Open Access Journals (Sweden)

Hideki Kitaura

2013-01-01

Full Text Available Tumor necrosis factor-α (TNF-α is a cytokine produced by monocytes, macrophages, and T cells and is induced by pathogens, endotoxins, or related substances. TNF-α may play a key role in bone metabolism and is important in inflammatory bone diseases such as rheumatoid arthritis. Cells directly involved in osteoclastogenesis include macrophages, which are osteoclast precursor cells, osteoblasts, or stromal cells. These cells express receptor activator of NF-κB ligand (RANKL to induce osteoclastogenesis, and T cells, which secrete RANKL, promote osteoclastogenesis during inflammation. Elucidating the detailed effects of TNF-α on bone metabolism may enable the identification of therapeutic targets that can efficiently suppress bone destruction in inflammatory bone diseases. TNF-α is considered to act by directly increasing RANK expression in macrophages and by increasing RANKL in stromal cells. Inflammatory cytokines such as interleukin- (IL- 12, IL-18, and interferon-γ (IFN-γ strongly inhibit osteoclast formation. IL-12, IL-18, and IFN-γ induce apoptosis in bone marrow cells treated with TNF-α  in vitro, and osteoclastogenesis is inhibited by the interactions of TNF-α-induced Fas and Fas ligand induced by IL-12, IL-18, and IFN-γ. This review describes and discusses the role of cells concerned with osteoclast formation and immunological reactions in TNF-α-mediated osteoclastogenesis in vitro and in vivo.

Cu-Mediated Stille Reactions of Sterically Congested Fragments: Towards the Total Synthesis of Zoanthamine

DEFF Research Database (Denmark)

Nielsen, Thomas E.; Le Quement, Sebastian; Juhl, Martin

2005-01-01

A study on the Stille reaction of alkenyl iodides and starmanes with structural resemblance to retrosynthetic fragments of a projected total synthesis of the marine alkaloid zoanthamine was carried out. A range of reaction conditions was examined, and a protocol developed by Corey utilizing excess...

Late adverse reactions to intravascular iodinated contrast media

International Nuclear Information System (INIS)

Webb, Judith A.W.; Stacul, Fulvio; Thomsen, Henrik S.; Morcos, Sameh K.

2003-01-01

Late adverse reactions to intravascular iodinated contrast media are defined as reactions occurring 1 h to 1 week after contrast medium injection. They have received increasing interest over the past decade, but their prevalence remains uncertain and their pathophysiology is not fully understood. The Contrast Media Safety Committee of the European Society of Urogenital Radiology decided to review the literature and to issue guidelines. An extensive literature search was carried out and summarized in a report. Based on the available information, simple guidelines have been drawn up. The report and guidelines were discussed at the 8th European Symposium on Urogenital Radiology in Genoa. Late adverse reactions after intravascular iodinated contrast medium include symptoms such as nausea, vomiting, headache, itching, skin rash, musculoskeletal pain, and fever. A significant proportion of these reactions is unrelated to the contrast medium; however, allergy-like skin reactions are well-documented side effects of contrast media with an incidence of approximately 2%. Late reactions appear to be commoner after non-ionic dimers. The majority of late skin reactions after contrast medium exposure are probably T-cell-mediated allergic reactions. Patients at increased risk of late skin reactions are those with a history of previous contrast medium reaction and those on interleukin-2 treatment. Most skin reactions are self-limiting and resolve within a week. Management is symptomatic and similar to the management of other drug-induced skin reactions. (orig.)

Effects of increasing doses of samarium-153-ethylenediaminetetramethylene phosphonate on axial and appendicular skeletal growth in juvenile rabbits

Energy Technology Data Exchange (ETDEWEB)

Essman, Stephanie C. [Department of Veterinary Medicine and Surgery, College of Veterinary Medicine, University of Missouri-Columbia, Columbia, MO 65211 (United States)], E-mail: essmans@missouri.edu; Lewis, Michael R. [Department of Veterinary Medicine and Surgery, College of Veterinary Medicine, University of Missouri-Columbia, Columbia, MO 65211 (United States); Department of Radiology, University of Missouri-Columbia, Columbia, MO 65211 (United States); Nuclear Science and Engineering Institute, University of Missouri-Columbia, Columbia, MO 65211 (United States); Research Service, Harry S. Truman Memorial Veterans' Hospital, Columbia, MO 65201 (United States); Fox, Derek B. [Department of Veterinary Medicine and Surgery, College of Veterinary Medicine, University of Missouri-Columbia, Columbia, MO 65211 (United States)

2008-02-15

Introduction: Targeted radiotherapy using samarium-153-ethylenediaminetetramethylene phosphonate ({sup 153}Sm-EDTMP) is currently under investigation for treatment of osteosarcoma. Osteosarcoma often occurs in children, and previous studies on a juvenile rabbit model demonstrated that clinically significant damage to developing physeal cartilage may occur as a result of systemic {sup 153}Sm-EDTMP therapy. The aim of this study was to evaluate the late effects of {sup 153}Sm-EDTMP on skeletal structures during growth to maturity and to determine if there is a dose response of {sup 153}Sm-EDTMP on growth of long bones. Methods: Female 8-week-old New Zealand white rabbits were divided into three treatment groups plus controls. Each rabbit was intravenously administered a predetermined dose of {sup 153}Sm-EDTMP. Multiple bones of each rabbit were radiographed every 2 months until physeal closure, with subsequent measurements made to assess for abbreviated bone growth. Statistical analyses were performed to determine the differences in bone length between groups, with significance set at P<.05. Results: Significant differences in lengths of multiple bones were detected between the high-dose group and other treatment groups and controls at each time interval. A significant difference in lengths of the tibias was also noted in the medium-treatment group, compared to controls. Mean reduction of bone length was first detected at 4 months and did not increase significantly over time. Conclusions: These data suggest that clinically significant bone shortening may occur as a result of high-dosage administration of {sup 153}Sm-EDTMP. Further investigation regarding the effects of bone-seeking radiopharmaceuticals on bone growth and physeal cartilage is warranted.

Longitudinal relations among parents' reactions to children's negative emotions, effortful control, and math achievement in early elementary school.

Science.gov (United States)

Swanson, Jodi; Valiente, Carlos; Lemery-Chalfant, Kathryn; Bradley, Robert H; Eggum-Wilkens, Natalie D

2014-01-01

Panel mediation models and fixed-effects models were used to explore longitudinal relations among parents' reactions to children's displays of negative emotions, children's effortful control (EC), and children's math achievement (N = 291; M age in fall of kindergarten = 5.66 years, SD = .39 year) across kindergarten through second grade. Parents reported their reactions and children's EC. Math achievement was assessed with a standardized achievement test. First-grade EC mediated the relation between parents' reactions at kindergarten and second-grade math achievement, beyond stability in constructs across study years. Panel mediation model results suggested that socialization of EC may be one method of promoting math achievement in early school; however, when all omitted time-invariant covariates of EC and math achievement were controlled, first-grade EC no longer predicted second-grade math achievement. © 2014 The Authors. Child Development © 2014 Society for Research in Child Development, Inc.

Loop mediated isothermal amplification assay using hydroxy naphthol blue, conventional polymerase chain reaction and real-time PCR in the diagnosis of intraocular tuberculosis

Directory of Open Access Journals (Sweden)

P K Balne

2015-01-01

Full Text Available This study is a comparative evaluation (Chi-square test of a closed tube loop mediated isothermal amplification assay using hydroxy naphthol blue dye (HNB-LAMP, real-time polymerase chain reaction (PCR and conventional PCR in the diagnosis of intraocular tuberculosis. Considering clinical presentation as the gold standard in 33 patients, the sensitivity of HNB-LAMP assay (75.8% was higher (not significant, P value 0.2 than conventional PCR (57.6% and lower than real-time PCR (90.9%. Specificity was 100% by all three methods. No amplification was observed in negative controls (n = 20 by all three methods. The cost of the HNB-LAMP assay was Rs. 500.00 and it does not require thermocycler, therefore, it can be used as an alternative to conventional PCR in resource-poor settings.

Ruphus-mediated Suzuki cross-coupling of secondary alkyl trifluoroborates

NARCIS (Netherlands)

Hoogenband, van den A.; Lange, J.H.M.; Terpstra, J.W.; Koch, M.; Visser, G.M.; Visser, de M.; Korstanje, T.J.; Jastrzebski, J.T.B.H.

2008-01-01

A Ruphos-mediated Suzuki cross-coupling between (hetero)aryl bromides and secondary alkyltrifluoroborates is described using palladium catalysis. The Ruphos ligand showed superior properties as compared to S-Phos in this type of reaction. This method constitutes a valuable extension to current

Detection of single-nucleotide polymorphisms using an ON-OFF switching of regenerated biosensor based on a locked nucleic acid-integrated and toehold-mediated strand displacement reaction.

Science.gov (United States)

Gao, Zhong Feng; Ling, Yu; Lu, Lu; Chen, Ning Yu; Luo, Hong Qun; Li, Nian Bing

2014-03-04

Although various strategies have been reported for single-nucleotide polymorphisms (SNPs) detection, development of a time-saving, specific, and regenerated electrochemical sensing platform still remains a realistic goal. In this study, an ON-OFF switching of a regenerated biosensor based on a locked nucleic acid (LNA)-integrated and toehold-mediated strand displacement reaction technique is constructed for detection of SNPs. The LNA-integrated and methylene blue-labeled capture probe with an external toehold is designed to switch on the sensing system. The mutant-type DNA probe completes complementary with the capture probe to trigger the strand displacement reaction, which switches off the sensing system. However, when the single-base mismatched wild-type DNA probe is presented, the strand displacement reaction cannot be achieved; therefore, the sensing system still keeps the ON state. This DNA sensor is stable over five reuses. We further testify that the LNA-integrated sequence has better recognition ability for SNPs detection compared to the DNA-integrated sequence. Moreover, this DNA senor exhibits a remarkable discrimination capability of SNPs among abundant wild-type targets and 6000-fold (m/m) excess of genomic DNA. In addition, it is selective enough in complex and contaminant-ridden samples, such as human urine, soil, saliva, and beer. Overall, these results demonstrate that this reliable DNA sensor is easy to be fabricated, simple to operate, and stable enough to be readily regenerated.

Effect of long-term fertilization on humic redox mediators in multiple microbial redox reactions.

Science.gov (United States)

Guo, Peng; Zhang, Chunfang; Wang, Yi; Yu, Xinwei; Zhang, Zhichao; Zhang, Dongdong

2018-03-01

This study investigated the effects of different long-term fertilizations on humic substances (HSs), humic acids (HAs) and humins, functioning as redox mediators for various microbial redox biotransformations, including 2,2',4,4',5,5'- hexachlorobiphenyl (PCB 153 ) dechlorination, dissimilatory iron reduction, and nitrate reduction, and their electron-mediating natures. The redox activity of HSs for various microbial redox metabolisms was substantially enhanced by long-term application of organic fertilizer (pig manure). As a redox mediator, only humin extracted from soils with organic fertilizer amendment (OF-HM) maintained microbial PCB 153 dechlorination activity (1.03 μM PCB 153 removal), and corresponding HA (OF-HA) most effectively enhanced iron reduction and nitrate reduction by Shewanella putrefaciens. Electrochemical analysis confirmed the enhancement of their electron transfer capacity and redox properties. Fourier transform infrared analysis showed that C=C and C=O bonds, and carboxylic or phenolic groups in HSs might be the redox functional groups affected by fertilization. This research enhances our understanding of the influence of anthropogenic fertility on the biogeochemical cycling of elements and in situ remediation ability in agroecosystems through microorganisms' metabolisms. Copyright © 2017 Elsevier Ltd. All rights reserved.

The structural change of lanthanum diiodide upon hydrogenation

International Nuclear Information System (INIS)

Ryazanov, M.; Simon, A.; Mattausch, Hj.; Kremer, R.K.

2004-01-01

Slowly heating LaI 2 under 1 atm hydrogen to 650 deg. C leads to LaI 2 H, analyzed as LaI 2 H 0.95(3) , accompanied by a structural change from tetragonal to hexagonal. Sharp reflections in the XRD pattern can be indexed in P6 3 /mmc with a=4.2158(7) A and c=15.508(3) A, however, diffuse reflections indicate a polytypic intergrowth of MoS 2 and NbS 2 type structures. The earlier determined miscibility gap between LaI 2 and LaI 2 H x (x∼0.5) is closely related to the change of the structure. The Pauli paramagnetism for LaI 2 , χ P = 43(2)x10 -6 cm 3 /mol, derived from measurements on LaI 2 and LaI 2 H is in good agreement with the value estimated from band structure calculations

Self-worth mediates the effects of violent loss on PTSD symptoms.

Science.gov (United States)

Mancini, Anthony D; Prati, Gabriele; Black, Sarah

2011-02-01

Although research has confirmed that violent losses can exacerbate grief reactions, few investigations have explored underlying mechanisms. In this study, the authors used a dataset on bereaved spouses and bereaved parents at 4- and 18-months postloss to examine the mediating effects of self-worth and worldviews (benevolence and meaningfulness beliefs). Persons bereaved by violent causes had significantly more posttraumatic stress disorder (PTSD), grief, and depression symptoms at 4- and 18-months postloss than persons bereaved by natural causes. Moreover, self-worth but not worldviews mediated the effects of violent loss on PTSD and depression symptoms cross sectionally and PTSD symptoms longitudinally. Findings underscore that self-views are a critical component of problematic reactions to violent loss, but fail to support the role of "shattered" worldviews. Copyright © 2011 International Society for Traumatic Stress Studies.

Preparation of plutonium waste forms with ICPP calcined high-level waste

Energy Technology Data Exchange (ETDEWEB)

Staples, B.A.; Knecht, D.A. [Lockheed Idaho Technologies Co., Idaho Falls, ID (United States); O`Holleran, T.P. [Argonne National Lab.-West, Idaho Falls, ID (United States)] [and others

1997-05-01

Glass and glass-ceramic forms developed for the immobilization of calcined high-level wastes generated by Idaho Chemical Processing Plant (ICPP) fuel reprocessing activities have been investigated for ability to immobilize plutonium and to simultaneously incorporate calcined waste as an anti-proliferation barrier. Within the forms investigated, crystallization of host phases result in an increased loading of plutonium as well as its incorporation into potentially more durable phases than the glass. The host phases were initially formed and characterized with cerium (Ce{sup +4}) as a surrogate for plutonium (Pu{sup +4}) and samarium as a neutron absorber for criticality control. Verification of the surrogate testing results were then performed replacing cerium with plutonium. All testing was performed with surrogate calcined high-level waste. The results of these tests indicated that a potentially useful host phase, based on zirconia, can be formed either by devitrification or solid state reaction in the glass studied. This phase incorporates plutonium as well as samarium and the calcined waste becomes part of the matrix. Its ease of formation makes it potentially useful in excess plutonium dispositioning. Other durable host phases for plutonium and samarium, including zirconolite and zircon have been formed from zirconia or alumina calcine through cold press-sintering techniques and hot isostatic pressing. Host phase formation experiments conducted through vitrification or by cold press-sintering techniques are described and the results discussed. Recommendations are given for future work that extends the results of this study.

Preparation of plutonium waste forms with ICPP calcined high-level waste

International Nuclear Information System (INIS)

Staples, B.A.; Knecht, D.A.; O'Holleran, T.P.

1997-05-01

Glass and glass-ceramic forms developed for the immobilization of calcined high-level wastes generated by Idaho Chemical Processing Plant (ICPP) fuel reprocessing activities have been investigated for ability to immobilize plutonium and to simultaneously incorporate calcined waste as an anti-proliferation barrier. Within the forms investigated, crystallization of host phases result in an increased loading of plutonium as well as its incorporation into potentially more durable phases than the glass. The host phases were initially formed and characterized with cerium (Ce +4 ) as a surrogate for plutonium (Pu +4 ) and samarium as a neutron absorber for criticality control. Verification of the surrogate testing results were then performed replacing cerium with plutonium. All testing was performed with surrogate calcined high-level waste. The results of these tests indicated that a potentially useful host phase, based on zirconia, can be formed either by devitrification or solid state reaction in the glass studied. This phase incorporates plutonium as well as samarium and the calcined waste becomes part of the matrix. Its ease of formation makes it potentially useful in excess plutonium dispositioning. Other durable host phases for plutonium and samarium, including zirconolite and zircon have been formed from zirconia or alumina calcine through cold press-sintering techniques and hot isostatic pressing. Host phase formation experiments conducted through vitrification or by cold press-sintering techniques are described and the results discussed. Recommendations are given for future work that extends the results of this study

INDIUM AND ZINC MEDIATED ONE-ATOM CARBOCYCLE ENLARGEMENT IN WATER. (R822668)

Science.gov (United States)

AbstractSix-, seven-, eight-membered rings are enlarged by one carbon-atom into seven-, eight- and nine-membered ring derivatives respectively, via indium or zinc mediated reactions in aqueous medium.

Efficient Indium-Mediated Dehalogenation of Aromatics in Ionic Liquid Media

Directory of Open Access Journals (Sweden)

Flavia C. Zacconi

2012-12-01

Full Text Available An efficient indium-mediated dehalogenation reaction of haloaromatics and haloheteroaromatics in ionic liquids has been studied. This method is simple and effective in the presence of [bmim]Br. Furthermore, this methodology is environmentally friendly compared with conventional ones.

Elaeocarpusin Inhibits Mast Cell-Mediated Allergic Inflammation

Directory of Open Access Journals (Sweden)

Min-Jong Kim

2018-06-01

Full Text Available Mast cells are major effector cells for allergic responses that act by releasing inflammatory mediators, such as histamine and pro-inflammatory cytokines. Accordingly, different strategies have been pursued to develop anti-allergic and anti-inflammatory candidates by regulating the function of mast cells. The purpose of this study was to determine the effectiveness of elaeocarpusin (EL on mast cell-mediated allergic inflammation. We isolated EL from Elaeocarpus sylvestris L. (Elaeocarpaceae, which is known to possess anti-inflammatory properties. For this study, various sources of mast cells and mouse anaphylaxis models were used. EL suppressed the induction of markers for mast cell degranulation, such as histamine and β-hexosaminidase, by reducing intracellular calcium levels. Expression of pro-inflammatory cytokines, such as tumor necrosis factor-α and IL-4, was significantly decreased in activated mast cells by EL. This inhibitory effect was related to inhibition of the phosphorylation of Fyn, Lyn, Syk, and Akt, and the nuclear translocation of nuclear factor-κB. To confirm the effect of EL in vivo, immunoglobulin E-mediated passive cutaneous anaphylaxis (PCA and ovalbumin-induced active systemic anaphylaxis (ASA models were induced. EL reduced the PCA reaction in a dose dependent manner. In addition, EL attenuated ASA reactions such as hypothemia, histamine release, and IgE production. Our results suggest that EL is a potential therapeutic candidate for allergic inflammatory diseases that acts via the inhibition of mast cell degranulation and expression of proinflammatory cytokines.

The intriguing enhancement of chloroperoxidase mediated one-electron oxidations by azide, a known active-site ligand

International Nuclear Information System (INIS)

Andrew, Daniel; Hager, Lowell; Manoj, Kelath Murali

2011-01-01

Highlights: ► Azide is a well known heme–enzyme active site ligand and inhibitor. ► Herein, azide is reported to enhance a set of heme–enzyme mediated reactions. ► This effect is disconnected from native enzyme–azide binding. ► Azide could enhance heme–enzyme reactions via a newly proposed mechanism. ► Azide contained in reagents could impact reaction outcomes in redox biochemistry. -- Abstract: Azide is a well-known inhibitor of heme–enzymes. Herein, we report the counter-intuitive observation that at some concentration regimes, incorporation of azide in the reaction medium enhances chloroperoxidase (CPO, a heme–enzyme) mediated one-electron abstractions from several substrates. A diffusible azidyl radical based mechanism is proposed for explaining the phenomenon. Further, it is projected that the finding could have significant impact on routine in situ or in vitro biochemistry studies involving heme–enzyme systems and azide.

The role of honor concerns in emotional reactions to offences

NARCIS (Netherlands)

Rodriguez Mosquera, P.M.; Manstead, A.S.R.; Fischer, A.H.

2002-01-01

nvestigated the role of honor concerns in mediating the effect of nationality and gender on the reported intensity of anger and shame in reaction to insult vignettes. Spain, an honor culture, and The Netherlands, where honor is of less central significance, were selected for comparison. A total of

A Closer Look at the Relationship between Justice Perceptions and Feedback Reactions: The role of the quality of the relationship with the supervisor

Directory of Open Access Journals (Sweden)

Marjolein Feys

2008-06-01

Full Text Available Two field studies were undertaken to investigate the nature of the relationship between justice perceptions and feedback reactions. Previous work suggests that the relationship between procedural justice and feedback reactions is mediated by the quality of the relationship with the supervisor. However, there are also good theoretical reasons to hypothesise that the relationship between justice perceptions and feedback reactions is moderated by relationship quality. Across two field studies, we found support for both mediated and moderated relationships. Results of the moderator analyses showed that the positive relationship between justice perceptions and feedback reactions was more pronounced for subordinates in a low-quality relationship with their supervisor. The present results provide useful suggestions for enhancing feedback reactions in organisations.

Reactive Transport Modeling of Microbe-mediated Fe (II) Oxidation for Enhanced Oil Recovery

Science.gov (United States)

Surasani, V.; Li, L.

2011-12-01

Microbially Enhanced Oil Recovery (MEOR) aims to improve the recovery of entrapped heavy oil in depleted reservoirs using microbe-based technology. Reservoir ecosystems often contain diverse microbial communities those can interact with subsurface fluids and minerals through a network of nutrients and energy fluxes. Microbe-mediated reactions products include gases, biosurfactants, biopolymers those can alter the properties of oil and interfacial interactions between oil, brine, and rocks. In addition, the produced biomass and mineral precipitates can change the reservoir permeability profile and increase sweeping efficiency. Under subsurface conditions, the injection of nitrate and Fe (II) as the electron acceptor and donor allows bacteria to grow. The reaction products include minerals such as Fe(OH)3 and nitrogen containing gases. These reaction products can have large impact on oil and reservoir properties and can enhance the recovery of trapped oil. This work aims to understand the Fe(II) oxidation by nitrate under conditions relevant to MEOR. Reactive transport modeling is used to simulate the fluid flow, transport, and reactions involved in this process. Here we developed a complex reactive network for microbial mediated nitrate-dependent Fe (II) oxidation that involves both thermodynamic controlled aqueous reactions and kinetic controlled Fe (II) mineral reaction. Reactive transport modeling is used to understand and quantify the coupling between flow, transport, and reaction processes. Our results identify key parameter controls those are important for the alteration of permeability profile under field conditions.

Theoretical and experimental insights into the ·OH-mediated mineralization mechanism of flutriafol

International Nuclear Information System (INIS)

Liu, Siqi; Zhou, Xiezhen; Han, Weiqing; Li, Jiansheng; Sun, Xiuyun; Shen, Jinyou; Wang, Lianjun

2017-01-01

Highlights: • A complete ·OH-mediated degradation pathway of flutriafol is proposed. • Computational approach is effective to reveal the favorable transformation process. • The electrochemical experiments well verify the theoretical results. - Abstract: Flutriafol is one of the widely used triazole fungicides in global pesticides market, and its degradation mechanisms are important to develop powerful technologies to remove it. Insight into the kinetics and mechanisms of ·OH-mediated mineralization of flutriafol have been obtained using quantum chemical calculation and electrochemical experiment methods. The complete ·OH-mediated degradation pathway of flutriafol was proposed by density functional theory (DFT) simulation and the potential energy surface was mapped out for possible reactions. On the basis of DFT calculations, the optimal ·OH-mediated mineralization mechanism of flutriafol was revealed, and a series of intermediates were observed accumulated in the degradation process, most significance among which were (2-fluorophenyl) (4-fluorophenyl)-Methanone, phenol, dihydroxybenzenes, benzoquinones, muconic acids, maleic acids, oxalic acids and formic acid. To give deeper insight into the ·OH-mediated reaction mechanism, the electrostatic potential (ESP) and average local ionization energy (ALIE) analysis were conducted for o-benzoquinone and p-benzoquinone. The proposed mechanism was further validated by electrochemical experiments at TiO_2-NTs/SnO_2-Sb/PbO_2 anode. The main intermediates were identified and quantified by experimental method, indicating that the proposed ·OH-mediated degradation mechanism derived from DFT calculations was feasible. These detailed findings could be instrumental for a comprehensive understanding of the ·OH-mediated mineralization mechanism of flutriafol and the similar contaminants.

User’s Guide for Biodegradation Reactions in TMVOCBio

Energy Technology Data Exchange (ETDEWEB)

Jung, Yoojin [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Battistelli, Alfredo [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

2017-08-31

TMVOCBio is an extended version of the TMVOC numerical reservoir simulator, with the capability of simulating multiple biodegradation reactions mediated by different microbial populations or based on different redox reactions, thus involving different electron acceptors. This modeling feature is implemented within the existing TMVOC module in iTOUGH2. TMVOCBio, originally developed by Battistelli (2003; 2004), uses a general modified form of the Monod kinetic rate equation to simulate biodegradation reactions, which effectively simulates the uptake of a substrate while accounting for various limiting factors (i.e., the limitation by substrate, electron acceptor, or nutrients). Two approaches are included: 1) a multiple Monod kinetic rate equation, which assumes all the limiting factors simultaneously affect the substrate uptake rate, and 2) a minimum Monod model, which assumes that the substrate uptake rate is controlled by the most limiting factor among those acting for the specific substrate. As the limiting factors, biomass growth inhibition, toxicity effects, as well as competitive and non-competitive inhibition effects are included. The temperature and moisture dependence of biodegradation reactions is also considered. This report provides mathematical formulations and assumptions used for modeling the biodegradation reactions, and describes additional modeling capabilities. Detailed description of input format for biodegradation reactions is presented along with sample problems.

Carbon–carbon bond cleavage for Cu-mediated aromatic trifluoromethylations and pentafluoroethylations

Directory of Open Access Journals (Sweden)

Tsuyuka Sugiishi

2015-12-01

Full Text Available This short review highlights the copper-mediated fluoroalkylation using perfluoroalkylated carboxylic acid derivatives. Carbon–carbon bond cleavage of perfluoroalkylated carboxylic acid derivatives takes place in fluoroalkylation reactions at high temperature (150–200 °C or under basic conditions to generate fluoroalkyl anion sources for the formation of fluoroalkylcopper species. The fluoroalkylation reactions, which proceed through decarboxylation or tetrahedral intermediates, are useful protocols for the synthesis of fluoroalkylated aromatics.

Graphene oxide-mediated rapid dechlorination of carbon tetrachloride by green rust

DEFF Research Database (Denmark)

Huang, Li-Zhi; Hansen, Hans Christian B.; Daasbjerg, Kim

2017-01-01

Graphene-based nanomaterials can mediate environmentally relevant abiotic redox reactions of chlorinated aliphatic hydrocarbons. In this study as low amounts as ∼0.007 % of graphene oxide (GO) was found to catalyze the reduction of carbon tetrachloride by layered Fe(II)-Fe(III) hydroxide (Green R....... This study indicates that traces of graphene oxide can affect reaction pathways as well as kinetics for dechlorination processes in anoxic sediments by facilitating a partial dechlorination....

Adverse reactions associated with acetylcysteine.

Science.gov (United States)

Sandilands, E A; Bateman, D N

2009-02-01

Paracetamol (acetaminophen) is one of the most common agents deliberately ingested in self-poisoning episodes and a leading cause of acute liver failure in the western world. Acetylcysteine is widely acknowledged as the antidote of choice for paracetamol poisoning, but its use is not without risk. Adverse reactions, often leading to treatment delay, are frequently associated with both intravenous and oral acetylcysteine and are a common source of concern among treating physicians. A systematic literature review investigating the incidence, clinical features, and mechanisms of adverse effects associated with acetylcysteine. A variety of adverse reactions to acetylcysteine have been described ranging from nausea to death, most of the latter due to incorrect dosing. The pattern of reactions differs with oral and intravenous dosing, but reported frequency is at least as high with oral as intravenous. The reactions to the intravenous preparation result in similar clinical features to true anaphylaxis, including rash, pruritus, angioedema, bronchospasm, and rarely hypotension, but are caused by nonimmunological mechanisms. The precise nature of this reaction remains unclear. Histamine now seems to be an important mediator of the response, and there is evidence of variability in patient susceptibility, with females, and those with a history of asthma or atopy are particularly susceptible. Quantity of paracetamol ingestion, measured through serum paracetamol concentration, is also important as higher paracetamol concentrations protect patients against anaphylactoid effects. Most anaphylactoid reactions occur at the start of acetylcysteine treatment when concentrations are highest. Acetylcysteine also affects clotting factor activity, and this affects the interpretation of minor disturbances in the International Normalized Ratio in the context of paracetamol overdose. This review discusses the incidence, clinical features, underlying pathophysiological mechanisms, and

Severe reactions to iodinated contrast agents: is anaphylaxis responsible?

International Nuclear Information System (INIS)

Dewachter, P.; Mouton-Faivre, C.

2001-01-01

The etiology of severe reactions following injection of iodinated contrast agent is the subject of controversy. No consensus has been established regarding the management of patients at risk, risk factors and pre-medication because in most cases published no diagnostic exploration has been carried out on patients who have experienced a severe reaction. Diagnosis of drug anaphylaxis is based on clinical history, proof of mediator release and drug specific IgE antibodies (when the technique is available) or cutaneous tests (when direct technique is not available). This approach has been adopted for etiologic diagnosis of 5 clinical cases of severe anaphylactoid reactions (including one death) following the injection of ionic and non ionic contrast agents. Clinical symptoms, biology and cutaneous tests are consistent with anaphylaxis. Any patient who has had a severe anaphylactoid reaction following injection of a contrast agent should undergo an allergology assessment to confirm the diagnosis and identify the culprit contrast agent. Indeed, no pre-medication has proved efficient for the prevention of subsequent allergic reactions. (author)

Fast prediction of cytochrome P450 mediated drug metabolism

DEFF Research Database (Denmark)

Rydberg, Patrik Åke Anders; Poongavanam, Vasanthanathan; Oostenbrink, Chris

2009-01-01

Cytochrome P450 mediated metabolism of drugs is one of the major determinants of their kinetic profile, and prediction of this metabolism is therefore highly relevant during the drug discovery and development process. A new rule-based method, based on results from density functional theory...... calculations, for predicting activation energies for aliphatic and aromatic oxidations by cytochromes P450 is developed and compared with several other methods. Although the applicability of the method is currently limited to a subset of P450 reactions, these reactions describe more than 90...

Mediation Analysis with Multiple Mediators.

Science.gov (United States)

VanderWeele, T J; Vansteelandt, S

2014-01-01

Recent advances in the causal inference literature on mediation have extended traditional approaches to direct and indirect effects to settings that allow for interactions and non-linearities. In this paper, these approaches from causal inference are further extended to settings in which multiple mediators may be of interest. Two analytic approaches, one based on regression and one based on weighting are proposed to estimate the effect mediated through multiple mediators and the effects through other pathways. The approaches proposed here accommodate exposure-mediator interactions and, to a certain extent, mediator-mediator interactions as well. The methods handle binary or continuous mediators and binary, continuous or count outcomes. When the mediators affect one another, the strategy of trying to assess direct and indirect effects one mediator at a time will in general fail; the approach given in this paper can still be used. A characterization is moreover given as to when the sum of the mediated effects for multiple mediators considered separately will be equal to the mediated effect of all of the mediators considered jointly. The approach proposed in this paper is robust to unmeasured common causes of two or more mediators.

Modelling toehold-mediated RNA strand displacement.

Science.gov (United States)

Šulc, Petr; Ouldridge, Thomas E; Romano, Flavio; Doye, Jonathan P K; Louis, Ard A

2015-03-10

We study the thermodynamics and kinetics of an RNA toehold-mediated strand displacement reaction with a recently developed coarse-grained model of RNA. Strand displacement, during which a single strand displaces a different strand previously bound to a complementary substrate strand, is an essential mechanism in active nucleic acid nanotechnology and has also been hypothesized to occur in vivo. We study the rate of displacement reactions as a function of the length of the toehold and temperature and make two experimentally testable predictions: that the displacement is faster if the toehold is placed at the 5' end of the substrate; and that the displacement slows down with increasing temperature for longer toeholds. Copyright © 2015 Biophysical Society. Published by Elsevier Inc. All rights reserved.

Ambient Mechanochemical Solid-State Reactions of Carbon Nanotubes and Their Reactions via Covalent Coordinate Bond in Solution

Science.gov (United States)

Kabbani, Mohamad A.

In its first part, this thesis deals with ambient mechanochemical solid-state reactions of differently functionalized multiple walled carbon nanotubes (MWCNTs) while in its second part it investigates the cross-linking reactions of CNTs in solution via covalent coordinate bonds with transitions metals and carboxylate groups decorating their surfaces. In the first part a series of mechanochemical reactions involving different reactive functionalities on the CNTs such as COOH/OH, COOH/NH2 and COCl/OH were performed. The solid-state unzipping of CNTs leading to graphene formation was confirmed using spectroscopic, thermal and electron microscopy techniques. The non-grapheme products were established using in-situ quadruple mass spectroscopy. The experimental results were confirmed by theoretical simulation calculations using the 'hot spots' protocol. The kinetics of the reaction between MWCNT-COOH and MWCNT-OH was monitored using variable temperature Raman spectroscopy. The low activation energy was discussed in terms of hydrogen bond mediated proton transfer mechanism. The second part involves the reaction of MWCNTII COOH with Zn (II) and Cu (II) to form CNT metal-organic frame (MOFs) products that were tested for their effective use as counter-electrodes in dyes sensitized solar cells (DSSC). The thesis concludes by the study of the room temperature reaction between the functionalized graphenes, GOH and G'-COOH followed by the application of compressive loads. The 3D solid graphene pellet product ( 0.6gm/cc) is conductive and reflective with a 35MPa ultimate strength as compared to 10MPa strength of graphite electrode ( 2.2gm/cc).

Platelet Vascular Endothelial Growth Factor is a Potential Mediator of Transfusion-Related Acute Lung Injury.

Science.gov (United States)

Maloney, James P; Ambruso, Daniel R; Voelkel, Norbert F; Silliman, Christopher C

The occurrence of non-hemolytic transfusion reactions is highest with platelet and plasma administration. Some of these reactions are characterized by endothelial leak, especially transfusion related acute lung injury (TRALI). Elevated concentrations of inflammatory mediators secreted by contaminating leukocytes during blood product storage may contribute to such reactions, but platelet-secreted mediators may also contribute. We hypothesized that platelet storage leads to accumulation of the endothelial permeability mediator vascular endothelial growth factor (VEGF), and that intravascular administration of exogenous VEGF leads to extensive binding to its lung receptors. Single donor, leukocyte-reduced apheresis platelet units were sampled over 5 days of storage. VEGF protein content of the centrifuged supernatant was determined by ELISA, and the potential contribution of VEGF from contaminating leukocytes was quantified. Isolated-perfused rat lungs were used to study the uptake of radiolabeled VEGF administered intravascularly, and the effect of unlabeled VEGF on lung leak. There was a time-dependent release of VEGF into the plasma fraction of the platelet concentrates (62 ± 9 pg/ml on day one, 149 ± 23 pg/ml on day 5; mean ± SEM, pproducts.

In silico prediction of potential chemical reactions mediated by human enzymes.

Science.gov (United States)

Yu, Myeong-Sang; Lee, Hyang-Mi; Park, Aaron; Park, Chungoo; Ceong, Hyithaek; Rhee, Ki-Hyeong; Na, Dokyun

2018-06-13

Administered drugs are often converted into an ineffective or activated form by enzymes in our body. Conventional in silico prediction approaches focused on therapeutically important enzymes such as CYP450. However, there are more than thousands of different cellular enzymes that potentially convert administered drug into other forms. We developed an in silico model to predict which of human enzymes including metabolic enzymes as well as CYP450 family can catalyze a given chemical compound. The prediction is based on the chemical and physical similarity between known enzyme substrates and a query chemical compound. Our in silico model was developed using multiple linear regression and the model showed high performance (AUC = 0.896) despite of the large number of enzymes. When evaluated on a test dataset, it also showed significantly high performance (AUC = 0.746). Interestingly, evaluation with literature data showed that our model can be used to predict not only enzymatic reactions but also drug conversion and enzyme inhibition. Our model was able to predict enzymatic reactions of a query molecule with a high accuracy. This may foster to discover new metabolic routes and to accelerate the computational development of drug candidates by enabling the prediction of the potential conversion of administered drugs into active or inactive forms.

Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts

Science.gov (United States)

Pacardo, Dennis B.; Slocik, Joseph M.; Kirk, Kyle C.; Naik, Rajesh R.; Knecht, Marc R.

2011-05-01

To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions.

Interrogating the catalytic mechanism of nanoparticle mediated Stille coupling reactions employing bio-inspired Pd nanocatalysts.

Science.gov (United States)

Pacardo, Dennis B; Slocik, Joseph M; Kirk, Kyle C; Naik, Rajesh R; Knecht, Marc R

2011-05-01

To address issues concerning the global environmental and energy state, new catalytic technologies must be developed that translate ambient and efficient conditions to heavily used reactions. To achieve this, the structure/function relationship between model catalysts and individual reactions must be critically discerned to identify structural motifs responsible for the reactivity. This is especially true for nanoparticle-based systems where this level of information remains limited. Here we present evidence indicating that peptide-capped Pd nanoparticles drive Stille C-C coupling reactions via Pd atom leaching. Through a series of reaction studies, the materials are shown to be optimized for reactivity under ambient conditions where increases in temperature or catalyst concentration deactivate reactivity due to the leaching process. A quartz crystal microbalance analysis demonstrates that Pd leaching occurs during the initial oxidative addition step at the nanoparticle surface by aryl halides. Together, this suggests that peptide-based materials may be optimally suited for use as model systems to isolate structural motifs responsible for the generation of catalytically reactive materials under ambient synthetic conditions. © The Royal Society of Chemistry 2011

The Influence of Receptor-Mediated Interactions on Reaction-Diffusion Mechanisms of Cellular Self-organisation

KAUST Repository

Klika, Vá clav; Baker, Ruth E.; Headon, Denis; Gaffney, Eamonn A.

2011-01-01

formation, motivating numerous theoretical and experimental studies, though its verification at the molecular level in biological systems has remained elusive. In this work, we consider the influence of receptor-mediated dynamics within the framework

Loop-mediated isothermal amplification (LAMP) shield for Arduino DNA detection

NARCIS (Netherlands)

Velders, Aldrik H.; Schoen, Cor; Saggiomo, Vittorio

2018-01-01

Objective: Loop-mediated isothermal amplification (LAMP) of DNA is gaining relevance as a method to detect nucleic acids, as it is easier, faster, and more powerful than conventional Polymerase Chain Reaction. However, LAMP is still mostly used in laboratory settings, because of the lack of a cheap

Methylation of the phosphate oxygen moiety of phospholipid-methoxy(polyethylene glycol) conjugate prevents PEGylated liposome-mediated complement activation and anaphylatoxin production

DEFF Research Database (Denmark)

Moghimi, S.M.; Hamad, I.; Andresen, Thomas Lars

2006-01-01

Methoxy(polyethylene glycol), mPEG, -grafted liposomes are known to exhibit prolonged circulation time in the blood, but their infusion into a substantial percentage of human subjects triggers immediate non-IgE-mediated hypersensitivity reactions. These reactions are strongly believed to arise from...... to PEGylated liposome-mediated complement activation. Our findings provide a rational conceptual basis for development of safer vesicles for site-specific drug delivery and controlled release at pathological sites....

Effect of samarium (Sm) addition on the microstructures and mechanical properties of Al–7Si–0.7Mg alloys

International Nuclear Information System (INIS)

Qiu, Hongxu; Yan, Hong; Hu, Zhi

2013-01-01

Highlights: •Sm affected the secondary dendrite arm spacing of Al–7Si–0.7Mg alloy. •The coarse plate-like eutectic silicon was fully modified into a fine branched and particle structure when 0.6 wt.% Sm added. •The tensile properties were enhanced by the addition of Sm. •Sm has marked effects on eutectic temperature and the latent heat ΔH R on remelting behavior. •The morphology and chemical composition of Sm-rich intermetallics were studied. -- Abstract: The effects of samarium (Sm) additions (0–0.9 wt.%) on the microstructures and mechanical properties of Al–7Si–0.7Mg alloys have been studied in this article. The microstructures of the as-cast samples were examined by optical microscopy (OM) and scanning electron microscopy (SEM). The experimental results indicated that the rare earth Sm affected the secondary dendrite arm spacing (SDAS) of Al–7Si–0.7Mg alloy. And it was found that Sm had great modification effects on the microstructures of eutectic silicon. When 0.6 wt.% Sm was added to the alloy, the coarse plate-like eutectic silicon was fully modified into a fine fibrous structure; the dendrites of Al–7Si–0.7Mg alloy was best refined. The mechanical properties were investigated by tensile test. The findings indicate that the tensile properties and elongation were improved by the addition of Sm. And a good combination of ultimate tensile strength (215 MPa) and elongation (3.3%) was obtained when the Sm addition was up to 0.6 wt.%. Furthermore the results of thermal analysis reveal that Sm addition had marked effects on eutectic temperature and the latent heat ΔH R on remelting behavior

Structural and superconducting properties of (Y,Gd)Ba2Cu3O7-δ grown by MOCVD on samarium zirconate buffered IBAD-MgO

International Nuclear Information System (INIS)

Stan, L; Holesinger, T G; Maiorov, B; Feldmann, D M; Usov, I O; DePaula, R F; Civale, L; Foltyn, S R; Jia, Q X; Chen, Y; Selvamanickam, V

2008-01-01

Textured samarium zirconate (SZO) films have been grown by reactive cosputtering directly on an ion beam assisted deposited (IBAD) MgO template, without an intermediate homoepitaxial MgO layer. The subsequent growth of 0.9 μm thick (Y,Gd)Ba 2 Cu 3 O 7-δ ((Y, Gd)BCO) films by metal organic chemical vapor deposition (MOCVD) yielded well textured films with a full width at half maximum of 1.9 0 and 3.4 0 for the out-of-plane and in-plane texture, respectively. Microstructural characterizations of the SZO buffered samples revealed clean interfaces. This indicates that the SZO not only provides a diffusion barrier, but also functions as a buffer for (Y, Gd)BCO grown by MOCVD. The achievement of self-field critical current densities (J c ) of over 2 MA cm -2 at 75.5 K is another proof of the effectiveness of SZO as a buffer on the IBAD-MgO template. The in-field measurements revealed an asymmetric angular dependence of J c and a shift of the ab-plane maxima due to the tilted nature of the template and (Y,Gd) 2 O 3 particles existing in the (Y, Gd)BCO matrix. The present results are especially important because they demonstrate that high temperature superconducting coated conductors with simpler architecture can be fabricated using commercially viable processes

[Pseudoallergic reactions. Intolerance to natural and synthetic food constituents masquerading as food allergy].

Science.gov (United States)

Kurek, M

1996-09-01

Adverse hypersensitivity reactions to natural foods and certain drugs and food additives are mediated by immunological (allergy) or non-immunological mechanisms. Some clinical and physiological similarities have been noted between these allergic and non-allergic reactions. This observation has led to the concept of "pseudoallergic reactions-PAR". PAR can be triggered in various ways such as: interactions with the central or peripherical nervous system, non-specific release of mediators, enzyme inhibition due to hereditary or pharmacologically induced enzyme deficiencies and pharmacological properties of some natural food constituents such as biogenic amines. The prevalence of adverse reactions to food additives has been calculated to be about 0.1%. PAR to food additives occurs frequently in patients suffering from urticaria, asthma and may be accompanied by history of aspirin or NSAI pseudoallergic reactions. The same additives (azo dyes, sulphites, benzoates) are used in various drug formulations and may be responsible for eliciting PAR. In Poland, labelling of food additives, following the "E number system", has been mandatory since 1993. Unfortunately, this satisfactory trend has not yet been applied to drug additives. The diagnosis of PAR to food additives is based on the anamnesis with analysis of the patient's drug and dietary intake. Skin tests and "in vitro" tests are only sporadically informative. In each individual patient, a specific challenge with additives is desirable. Food additives may be tested according to the schedule based on DBPCFC principle. Individually performed exclusion regimes are the principal methods of prevention.

Mast cell function modulating IgE-mediated allergy

Directory of Open Access Journals (Sweden)

Ruby Pawankar

1999-01-01

Full Text Available Allergic diseases, such as atopic rhinitis, bronchial asthma and urticaria, are prevalent and increasing in frequency. Mast cells are known to play a central role in the immediate phase reaction of allergic diseases through the IgE-mediated release of a variety of chemical mediators, such as histamine, leukotrienes and prostaglandins. In contrast, T lymphocytes, basophils and eosinophils are thought to be responsible for inducing the late phase response. However, whether the mast cell can be simplistically assigned a role in the immediate phase allergic response and whether mast cells are necessary for the ongoing allergic response, including the development of hyperresponsiveness, remains to be completely studied. In the present article, the author will discuss the integrated roles of mast cells in IgE-mediated allergic inflammation, with specific emphasis on the roles of mast cell-derived cytokines in the late phase allergic response and chronic allergic inflammation.

Sorption of samarium in soils: influence of soil properties and Sm concentration

Energy Technology Data Exchange (ETDEWEB)

Ramirez-Guinart, Oriol; Salaberria, Aitor; Rigol, Anna; Vidal, Miquel [Analytical Chemistry department, Faculty of Chemistry, University of Barcelona, Marti i Franques 1-11, 08028, Barcelona (Spain)

2014-07-01

Due to the fact that barriers of Deep Geological Repositories (DGR) may lose efficiency before the radioisotopes present in the High Level Radioactive Waste (HLRW) completely decay, it is possible that, in the long-term, radioactive leachates may escape from the DGR and reach the soil and water compartments in the biosphere. Therefore, it is required to examine the interaction and mobility of radionuclides present in the HLRW, or their chemical analogues, to predict the impact of their eventual incorporation in the biosphere and to assess the derived risk. Although relevant data have been recently obtained for a few radionuclides in soils, there are still some important gaps for some radionuclides, such us for samarium (Sm). Sm is a lanthanide that, besides being considered as a natural analogue of actinides, may also be present in HLRW in the form of the radioactive isotope {sup 151}Sm. The main objective of this work was to obtain sorption data (K{sub d}) of {sup 151}Sm gathered from a set of soil samples physicochemical fully-characterized (pH, texture, cationic exchange capacity, soil solution cationic composition, organic matter, carbonate and metallic oxides content, etc.). Additionally, as an alternative for testing sorption capacity of radionuclides in soils is the use of the corresponding stable isotope or a chemical analogue, the influence of Sm concentration was also checked. To evaluate {sup 151}Sm sorption, batch assays were carried out for each soil sample, which consisted in a pre-equilibration step of 2 g of each soil with 50 ml of double deionised water, and a subsequent equilibration step with the same solution, but labelled with {sup 151}Sm. The activity of {sup 151}Sm in initial and final solutions was measured by liquid scintillation and K{sub d} ({sup 151}Sm) data were calculated. The reversibly sorbed fraction was estimated by the application of a single extraction test, with double deionised water, to soil residues coming from the previous

A flow reactor setup for photochemistry of biphasic gas/liquid reactions

Directory of Open Access Journals (Sweden)

Josef Schachtner

2016-08-01

Full Text Available A home-built microreactor system for light-mediated biphasic gas/liquid reactions was assembled from simple commercial components. This paper describes in full detail the nature and function of the required building elements, the assembly of parts, and the tuning and interdependencies of the most important reactor and reaction parameters. Unlike many commercial thin-film and microchannel reactors, the described set-up operates residence times of up to 30 min which cover the typical rates of many organic reactions. The tubular microreactor was successfully applied to the photooxygenation of hydrocarbons (Schenck ene reaction. Major emphasis was laid on the realization of a constant and highly reproducible gas/liquid slug flow and the effective illumination by an appropriate light source. The optimized set of conditions enabled the shortening of reaction times by more than 99% with equal chemoselectivities. The modular home-made flow reactor can serve as a prototype model for the continuous operation of various other reactions at light/liquid/gas interfaces in student, research, and industrial laboratories.

Scandium(III) catalysis of transimination reactions. Independent and constitutionally coupled reversible processes.

Science.gov (United States)

Giuseppone, Nicolas; Schmitt, Jean-Louis; Schwartz, Evan; Lehn, Jean-Marie

2005-04-20

Sc(OTf)(3) efficiently catalyzes the self-sufficient transimination reaction between various types of C=N bonds in organic solvents, with turnover frequencies up to 3600 h(-)(1) and rate accelerations up to 6 x 10(5). The mechanism of the crossover reaction in mixtures of amines and imines is studied, comparing parallel individual reactions with coupled equilibria. The intrinsic kinetic parameters for isolated reactions cannot simply be added up when several components are mixed, and the behavior of the system agrees with the presence of a unique mediator that constitutes the core of a network of competing reactions. In mixed systems, every single amine or imine competes for the same central hub, in accordance with their binding affinity for the catalyst metal ion center. More generally, the study extends the basic principles of constitutional dynamic chemistry to interconnected chemical transformations and provides a step toward dynamic systems of increasing complexity.

Gold nanoparticle-mediated laser stimulation causes a complex stress signal in neuronal cells

Science.gov (United States)

Johannsmeier, Sonja; Heeger, Patrick; Terakawa, Mitsuhiro; Kalies, Stefan; Heisterkamp, Alexander; Ripken, Tammo; Heinemann, Dag

2017-07-01

Gold nanoparticle mediated laser stimulation of neuronal cells allows for cell activation on a single-cell level. It could therefore be considered an alternative to classical electric neurostimulation. The physiological impact of this new approach has not been intensively studied so far. Here, we investigate the targeted cell's reaction to a laser stimulus based on its calcium response. A complex cellular reaction involving multiple sources has been revealed.

Perceived Control and Psychological Contract Breach as Explanations of the Relationships Between Job Insecurity, Job Strain and Coping Reactions: Towards a Theoretical Integration.

Science.gov (United States)

Vander Elst, Tinne; De Cuyper, Nele; Baillien, Elfi; Niesen, Wendy; De Witte, Hans

2016-04-01

This study aims to further knowledge on the mechanisms through which job insecurity is related to negative outcomes. Based on appraisal theory, two explanations-perceived control and psychological contract breach-were theoretically integrated in a comprehensive model and simultaneously examined as mediators of the job insecurity-outcome relationship. Different categories of outcomes were considered, namely work-related (i.e. vigour and need for recovery) and general strain (i.e. mental and physical health complaints), as well as psychological (i.e. job satisfaction and organizational commitment) and behavioural coping reactions (i.e. self-rated performance and innovative work behaviour). The hypotheses were tested using data of a heterogeneous sample of 2413 Flemish employees by means of both single and multiple mediator structural equation modelling analyses (bootstrapping method). Particularly, psychological contract breach accounted for the relationship between job insecurity and strain. Both perceived control and psychological contract breach mediated the relationships between job insecurity and psychological coping reactions, although the indirect effects were larger for psychological contract breach. Finally, perceived control was more important than psychological contract breach in mediating the relationships between job insecurity and behavioural coping reactions. This study meets previous calls for a theoretical integration regarding mediators of the job insecurity-outcome relationship. Copyright © 2014 John Wiley & Sons, Ltd.

Development of interactive graphic user interfaces for modeling reaction-based biogeochemical processes in batch systems with BIOGEOCHEM

Science.gov (United States)

Chang, C.; Li, M.; Yeh, G.

2010-12-01

The BIOGEOCHEM numerical model (Yeh and Fang, 2002; Fang et al., 2003) was developed with FORTRAN for simulating reaction-based geochemical and biochemical processes with mixed equilibrium and kinetic reactions in batch systems. A complete suite of reactions including aqueous complexation, adsorption/desorption, ion-exchange, redox, precipitation/dissolution, acid-base reactions, and microbial mediated reactions were embodied in this unique modeling tool. Any reaction can be treated as fast/equilibrium or slow/kinetic reaction. An equilibrium reaction is modeled with an implicit finite rate governed by a mass action equilibrium equation or by a user-specified algebraic equation. A kinetic reaction is modeled with an explicit finite rate with an elementary rate, microbial mediated enzymatic kinetics, or a user-specified rate equation. None of the existing models has encompassed this wide array of scopes. To ease the input/output learning curve using the unique feature of BIOGEOCHEM, an interactive graphic user interface was developed with the Microsoft Visual Studio and .Net tools. Several user-friendly features, such as pop-up help windows, typo warning messages, and on-screen input hints, were implemented, which are robust. All input data can be real-time viewed and automated to conform with the input file format of BIOGEOCHEM. A post-processor for graphic visualizations of simulated results was also embedded for immediate demonstrations. By following data input windows step by step, errorless BIOGEOCHEM input files can be created even if users have little prior experiences in FORTRAN. With this user-friendly interface, the time effort to conduct simulations with BIOGEOCHEM can be greatly reduced.

Stratum corneum profiles of inflammatory mediators in patch test reactions to common contact allergens and sodium lauryl sulfate

NARCIS (Netherlands)

Koppes, S. A.; Ljubojevic Hadzavdic, S.; Jakasa, I.; Franceschi, N.; Jurakić Tončić, R.; Marinović, B.; Brans, R.; Gibbs, S.; Frings-Dresen, M. H. W.; Rustemeyer, T.; Kezic, S.

2017-01-01

Background Recent studies have demonstrated allergen-specific differences in the gene expression of inflammatory mediators in patch tested skin. Objectives To determine levels of various inflammatory mediators in the stratum corneum (SC) after patch testing with common contact allergens and the skin

Accumulation of 111In-neutrophils in rabbit skin in allergic and non-allergic inflammatory reactions in vivo. Inhibition by neutrophil pretreatment in vitro with a monoclonal antibody recognizing the CD18 antigen

International Nuclear Information System (INIS)

Nourshargh, S.; Rampart, M.; Hellewell, P.G.; Jose, P.J.; Harlan, J.M.; Edwards, A.J.; Williams, T.J.

1989-01-01

The mAb 60.3 recognizes the neutrophil CD18 Ag. We have investigated the effect of in vitro pretreatment of radiolabeled neutrophils with mAb 60.3 on their accumulation in vivo. Further, we have compared the in vivo effects of mAb 60.3 with its effects on neutrophil adherence in vitro. Neutrophil accumulation in vivo was measured in response to: (1) exogenous mediators FMLP, C5a des Arg, LTB4 and IL-1; (2) endogenous mediators generated in a non-allergic inflammatory reaction induced by zymosan; and (3) endogenous mediators generated in two allergic inflammatory reactions, a passive cutaneous anaphylactic reaction and a reversed passive Arthus reaction in rabbit skin. Pretreatment of neutrophils with mAb 60.3 inhibited their accumulation in all the responses. The results demonstrate that there is a common mechanism mediating neutrophil accumulation in these inflammatory reactions. Neutrophils pretreated with mAb 60.3 were also unresponsive to chemoattractants in in vitro adherence assays. However, the antibody-treated neutrophils responded normally to FMLP and C5a with respect to granular enzyme release. These results suggest that the basal expression of CD18 Ag is important for the adherence of neutrophils to microvascular endothelial cells stimulated by the local generation, or administration, of chemical mediators in vivo. Despite the fact that mediators such as FMLP can increase CD18 expression in vitro, it appears more likely that such mediators act in vivo by inducing a conformational change in the basally expressed neutrophil adhesive molecules

Gender Differences in the Psychosomatic Reactions of Students Subjected to Examination Stress

Science.gov (United States)

Kosmala-Anderson, Joanna; Wallace, Louise M.

2007-01-01

Introduction: The study investigated pre-examination anxiety and emotional control strategies as possible mediators of gender differences in self reported intensity and type of psychosomatic reactions to examination stress. Method: Sample comprised 150 male and 150 female high school senior students and university students who voluntarily…

Nonimmediate hypersensitivity reactions to iodinated contrast media.

Science.gov (United States)

Gómez, Enrique; Ariza, Adriana; Blanca-López, Natalia; Torres, Maria J

2013-08-01

To provide a detailed analysis of the latest findings on the mechanisms underlying the nonimmediate reactions to iodinated contrast media and comment on the recent advances in diagnosis, focusing on the roles of the skin test, drug provocation test (DPT), and lymphocyte transformation test (LTT). Several studies have reported new findings supporting an important role for T-lymphocytes in the nonimmediate reactions to iodinated contrast media. The LTT has been used as an in-vitro tool for diagnosis, but with variable results. However, the inclusion of autologous monocyte-derived dendritic cells as professional antigen-presenting cells has improved the sensitivity of this test. Regarding in-vivo diagnosis, although skin testing has been routine, it has now been shown that its sensitivity and negative predictive value are low. Recent studies have demonstrated that the DPT is a well tolerated and useful procedure that is necessary to confirm the diagnosis of nonimmediate hypersensitivity reactions to iodinated contrast media. Nonimmediate reactions to contrast media are usually T-cell mediated. Diagnosis is based on skin testing, although its sensitivity and negative predictive value are not optimal. Consequently, drug provocation testing is often needed to confirm the diagnosis and also to seek alternative contrast media that can be tolerated.

Cyclopropenes in Metallacycle-Mediated Cross-Coupling with Alkynes: Convergent Synthesis of Highly Substituted Vinylcyclopropanes.

Science.gov (United States)

O'Rourke, Natasha F; Micalizio, Glenn C

2016-03-18

Stereodivergent metallacycle-mediated cross-coupling reactions are described for the synthesis of densely functionalized vinylcyclopropanes from the union of alkynes with cyclopropenes. Strategies explored include hydroxyl-directed and nondirected processes, with the latter of these delivering vinylcyclopropanes with exquisite levels of regio- and stereoselectivity. Challenges inherent to these coupling reactions include diastereoselectivity (with respect to the cyclopropene) and regioselectivity (with respect to both coupling partners).

Radical O-O coupling reaction in diferrate-mediated water oxidation studied using multireference wave function theory.

Science.gov (United States)

Kurashige, Yuki; Saitow, Masaaki; Chalupský, Jakub; Yanai, Takeshi

2014-06-28

The O-O (oxygen-oxygen) bond formation is widely recognized as a key step of the catalytic reaction of dioxygen evolution from water. Recently, the water oxidation catalyzed by potassium ferrate (K2FeO4) was investigated on the basis of experimental kinetic isotope effect analysis assisted by density functional calculations, revealing the intramolecular oxo-coupling mechanism within a di-iron(vi) intermediate, or diferrate [Sarma et al., J. Am. Chem. Soc., 2012, 134, 15371]. Here, we report a detailed examination of this diferrate-mediated O-O bond formation using scalable multireference electronic structure theory. High-dimensional correlated many-electron wave functions beyond the one-electron picture were computed using the ab initio density matrix renormalization group (DMRG) method along the O-O bond formation pathway. The necessity of using large active space arises from the description of complex electronic interactions and varying redox states both associated with two-center antiferromagnetic multivalent iron-oxo coupling. Dynamic correlation effects on top of the active space DMRG wave functions were additively accounted for by complete active space second-order perturbation (CASPT2) and multireference configuration interaction (MRCI) based methods, which were recently introduced by our group. These multireference methods were capable of handling the double shell effects in the extended active space treatment. The calculations with an active space of 36 electrons in 32 orbitals, which is far over conventional limitation, provide a quantitatively reliable prediction of potential energy profiles and confirmed the viability of the direct oxo coupling. The bonding nature of Fe-O and dual bonding character of O-O are discussed using natural orbitals.

On the Dehydrocoupling of Alkenylacetylenes Mediated by Various Samarocene Complexes: A Charming Story of Metal Cooperativity Revealing a Novel Dual Metal σ-Bond Metathesis Type of Mechanism (DM|σ-BM

Directory of Open Access Journals (Sweden)

Christos E. Kefalidis

2015-12-01

Full Text Available The prevailing reductive chemistry of Sm(II has been accessed and explored mostly by the use of samarocene precursors. The highly reducing character of these congeners, along with their Lewis acidity and predominantly ionic bonding, allows for the relatively facile activation of C–H bonds, as well as peculiar transformations of unsaturated substrates (e.g., C–C couplings. Among other important C–C coupling reactions, the reaction of phenylacetylene with different mono- or bimetallic samarocene complexes affords trienediyl complexes of the type {[(C5Me52Sm]2(µ-η2:η2-PhC4Ph}. In contrast, when t-butylacetylene is used, uncoupled monomers of the type (C5Me52Sm(C≡C–tBu were obtained. Although this type of reactivity may appear to be simple, the mechanism underlying these transformations is complex. This conclusion is drawn from the density functional theory (DFT mechanistic studies presented herein. The operating mechanistic paths consist of: (i the oxidation of each samarium center and the concomitant double reduction of the alkyne to afford a binuclear intermediate; (ii the C–H scission of the acetylinic bond that lies in between the two metals; (iii a dual metal σ-bond metathesis (DM|σ-SBM process that releases H2; and eventually (iv the C–C coupling of the two bridged μ-alkynides to give the final bimetallic trienediyl complexes. For the latter mechanistic route, the experimentally used phenylacetylene was considered first as well as the aliphatic hex-1-yne. More interestingly, we shed light into the formation of the mono(alkynide complex, being the final experimental product of the reaction with t-butylacetylene.

Role of β-h elimination in rhodium-mediated carbene insertion polymerization

NARCIS (Netherlands)

Finger, M.; Reek, J.N.H.; de Bruin, B.

2011-01-01

The importance of β-H elimination as a possible mechanism to induce chain termination/transfer and/or the formation of stereodefects in the Rh(diene)-mediated oligomerization and polymerization of carbenes has been studied by means of different approaches. As a remarkable feature, this reaction is

Visible-light-mediated selective arylation of cysteine in batch and flow

NARCIS (Netherlands)

Bottecchia, C.; Rubens, M.; Gunnoo, S.B.; Hessel, V.; Madder, A.

2017-01-01

A mild visible-light-mediated strategy for cysteine arylation is presented. The method relies on the use of eosin Y as a metal-free photocatalyst and aryldiazonium salts as arylating agents. The reaction can be significantly accelerated in a microflow reactor, whilst allowing the in situ formation

Evaluation of colonoscopic allergen provocation as a diagnostic tool in dogs with proven food hypersensitivity reactions.

Science.gov (United States)

Allenspach, K; Vaden, S L; Harris, T S; Gröne, A; Doherr, M G; Griot-Wenk, M E; Bischoff, S C; Gaschen, F

2006-01-01

To evaluate the colonoscopic allergen provocation (COLAP) test as a new tool for the diagnosis of IgE-mediated food allergy. Oral food challenges as well as COLAP testing were performed in a colony of nine research dogs with proven immediate-type food allergic reactions. In addition, COLAP was performed in five healthy dogs. When compared with the oral challenge test, COLAP accurately determined 18 of 23 (73 per cent) positive oral challenge reactions (73 per cent) in dogs with food allergies and was negative in the healthy dogs. The accuracy of this new test may be higher than that for gastric sensitivity testing. Therefore, COLAP holds promise as a new test to confirm the diagnosis of suspect IgE-mediated food allergy in dogs.

Humic substances-mediated microbial reductive dehalogenation of triclosan

Science.gov (United States)

Wang, L.; Xu, S.; Yang, Y.

2015-12-01

The role of natural organic matter in regulating the redox reactions as an electron shuttle has received lots of attention, because it can significantly affect the environmental degradation of contaminants and biogeochemical cycles of major elements. However, up to date, limited studies examined the role of natural organic matter in affecting the microbial dehalogenation of emergent organohalides, a critical detoxification process. In this study, we investigated the humic substance (HS)-mediated microbial dehalogenation of triclosan, a widely used antimicrobial agent. We found that the presence of HS stimulated the microbial degradation of triclosan by Shewanella putrefaciens CN-32. In the absence of HS, the triclosan was degraded gradually, achieving 8.6% residual at 8 days. With HS, the residual triclosan was below 2% after 4 days. Cl- was confirmed by ion chromatography analysis, but the dehalogenation processes and other byproducts warrant further investigations. The impact of HS on the degradation of triclosan was highly dependent on the concentration of HS. When the HS was below 15 mg/L, the degradation rate constant for triclosan increased with the organic carbon concentration. Beyond that point, the increased organic carbon concentration decreased the degradation of triclosan. Microbially pre-reduced HS abiotically reduced triclosan, testifying the electron shuttling processes. These results indicate that dissolved organic matter plays a dual role in regulating the degradation of triclosan: it mediates electron transport and inhibits the bioavailability through complexation. Such novel organic matter-mediated reactions for organohalides are important for evaluating the natural attenuation of emergent contaminants and designing cost-effective engineering treatment.

Genetics of immune-mediated disorders : from genome-wide association to molecular mechanism

NARCIS (Netherlands)

Kumar, Vinod; Wijmenga, Cisca; Xavier, Ramnik J.

2014-01-01

Genetic association studies have identified not only hundreds of susceptibility loci to immune-mediated diseases but also pinpointed causal amino-acid variants of HLA genes that contribute to many autoimmune reactions. Majority of non-HLA genetic variants are located within non-coding regulatory

Allergic reactions to raw, pasteurized, and homogenized/pasteurized cow milk

DEFF Research Database (Denmark)

Høst, A; Samuelsson, E G

1988-01-01

Five children aged 12-40 months with IgE-mediated adverse reactions to cow milk (immediate onset clinical pattern of cow milk allergy) were orally challenged double-blind in random order with three different milk preparations processed from the same batch of milk 1) raw untreated cow milk, 2......) pasteurized cow milk, 3) homogenized and pasteurized cow milk, and 4) Nutramigen (a commercial hypoallergenic infant formula based on hydrolysed casein) as placebo. Skin prick tests with the same preparations were also performed. On oral challenge the three different processed milk types provoked significant...... and similar allergic reactions in each child, and no adverse reactions followed the challenge with placebo (Nutramigen). Skin prick test with the same milk products were positive in all children and comparable to the results with an extract of purified raw cow milk protein (Soluprick), whereas Nutramigen did...

The effect of samarium doping on structure and enhanced thermionic emission properties of lanthanum hexaboride fabricated by spark plasma sintering

Energy Technology Data Exchange (ETDEWEB)

Zhou, Shenlin; Hu, Qianglin [College of Mathematics and Physics, Jinggangshan University, Jian (China); Zhang, Jiuxing; Liu, Danmin [Key Laboratory of Advanced Functional Materials, Ministry of Education, College of Materials Science and Engineering, Beijing University of Technology, Beijing (China); Huang, Qingzhen [NIST Center for Neutron Research, National Institute of Standards and Technology, MD (United States)

2014-03-15

Single-phase polycrystalline solid solutions (La{sub 1-x}Sm{sub x})B{sub 6} (x = 0, 0.2, 0.4, 0.8, 1) are fabricated by spark plasma sintering (SPS). This study demonstrates a systematic investigation of structure-property relationships in Sm-doped LaB{sub 6} ternary rare-earth hexaborides. The microstructure, crystallographic orientation, electrical resistivity, and thermionic emission performance of these compounds are investigated. Analysis of the results indicates that samarium (Sm) doping has a noticeable effect on the structure and performance of lanthanum hexaboride (LaB{sub 6}). The analytical investigation of the electron backscatter diffraction confirms that (La{sub 0.6}Sm{sub 0.4})B{sub 6} exhibits a clear (001) texture that results in a low work function. Work functions are determined by pulsed thermionic diode measurements at 1500-1873 K. The (La{sub 0.6}Sm{sub 0.4})B{sub 6} possesses improved thermionic emission properties compared to LaB{sub 6}. The current density of (La{sub 0.6}Sm{sub 0.4})B{sub 6} is 42.4 A cm{sup -2} at 1873 K, which is 17.5% larger than that of LaB{sub 6}. The values of Φ{sub R} for (La{sub 0.6}Sm{sub 0.4})B{sub 6} and LaB{sub 6} are 1.98 ± 0.03 and 1.67 ± 0.03 eV, respectively. Furthermore, the Sm substitution of lanthanum (La) effectively increases the electrical resistivity. These results reveal that Sm doping lead to significantly enhanced thermionic emission properties of LaB{sub 6}. The compound (La{sub 0.6}Sm{sub 0.4})B{sub 6} appears most promising as a future emitter material. (copyright 2014 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

X-ray-mediated cross linking of protein and DNA

International Nuclear Information System (INIS)

Minsky, B.D.; Braun, A.

1977-01-01

Using a simple filter assay for the binding of BSA or lysozyme to DNA, two mechanisms of x-ray-mediated cross linking are shown to occur. One, a fast reaction, appears to involve a radical intermediate, is inhibited by high pH and salt, and seems to be enhanced by deoxygenation. The second mechanism, a slow time-dependent component, differs from the fast reaction in its stimulation by histidine, its inhibition by catalase, and the lack of an oxygen effect. Separate irradiation of DNA or water does not lead to cross linking. However, separate irradiation of protein leads to cross linking which proceeds with slow-component kinetics

The catalytic potency of ß-glucosidase from Pyroccus furiosus in the direct glucosylation reaction

NARCIS (Netherlands)

Roode, de B.M.; Meer, van der T.D.; Kaper, T.; Franssen, M.C.R.; Padt, van der A.; Oost, van der J.; Boom, R.M.

2001-01-01

Enzymes from extremophiles operate at conditions that are different from their `normal' counterparts, and are therefore a useful extension of the enzyme toolbox. In this paper, the direct glucosylation reaction mediated by a hyperthermophilic -glucosidase from Pyrocuccus furiosus was investigated.

Modelling and simulation of a transketolase mediated reaction: Sensitivity analysis of kinetic parameters

DEFF Research Database (Denmark)

Sayar, N.A.; Chen, B.H.; Lye, G.J.

2009-01-01

In this paper we have used a proposed mathematical model, describing the carbon-carbon bond format ion reaction between beta-hydroxypyruvate and glycolaldehyde to synthesise L-erythrulose, catalysed by the enzyme transketolase, for the analysis of the sensitivity of the process to its kinetic...

Organophotocatalysis: Insights into the Mechanistic Aspects of Thiourea-Mediated Intermolecular [2+2] Photocycloadditions.

Science.gov (United States)

Vallavoju, Nandini; Selvakumar, Sermadurai; Pemberton, Barry C; Jockusch, Steffen; Sibi, Mukund P; Sivaguru, Jayaraman

2016-04-25

Mechanistic investigations of the intermolecular [2+2] photocycloaddition of coumarin with tetramethylethylene mediated by thiourea catalysts reveal that the reaction is enabled by a combination of minimized aggregation, enhanced intersystem crossing, and altered excited-state lifetime(s). These results clarify how the excited-state reactivity can be manipulated through catalyst-substrate interactions and reveal a third mechanistic pathway for thiourea-mediated organo-photocatalysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactions of N2O5 with Salty and Surfactant-Coated Glycerol: Interfacial Conversion of Br- to Br2 Mediated by Alkylammonium Cations.

Science.gov (United States)

Shaloski, Michael A; Gord, Joseph R; Staudt, Sean; Quinn, Sarah L; Bertram, Timothy H; Nathanson, Gilbert M

2017-05-18

Gas-liquid scattering and product-yield experiments are used to investigate reactions of N 2 O 5 with glycerol containing Br - and surfactant ions. N 2 O 5 oxidizes Br - to Br 2 for every solution tested: 2.7 M NaBr, 0.03 M tetrahexylammonium bromide (THABr), 0.03 M THABr + 0.5 M NaBr, 0.03 M THABr + 0.5 M NaCl, 0.03 M THABr + 0.01 M sodium dodecyl sulfate (SDS), and 0.01 M cetyltrimethylammonium bromide (CTABr). N 2 O 5 also reacts with glycerol itself to produce mono- and dinitroglycerin. Surface tension measurements indicate that 0.03 M THABr and 2.7 M NaBr have similar interfacial Br - concentrations, though their bulk Br - concentrations differ by 90-fold. We find that twice as much Br 2 is produced in the presence of THA + , implying that the conversion of Br - to Br 2 is initiated at the interface, perhaps mediated by the charged, hydrophobic pocket within the surface THA + cation. The addition of 0.5 M NaBr, 0.5 M NaCl, or 0.01 M SDS to 0.03 M THABr lowers the Br 2 production rate by 23%, 63%, and 67% of the THABr value, respectively. When CTA + is substituted for THA + , Br 2 production drops to 12% of the THABr value. The generation of Br 2 under such different conditions implies that trace amounts of surface-active alkylammonium ions can catalyze interfacial N 2 O 5 reactions, even when salts and other surfactants are present.

Samarium Polystibides Derived from Highly Activated Nanoscale Antimony.

Science.gov (United States)

Schoo, Christoph; Bestgen, Sebastian; Egeberg, Alexander; Klementyeva, Svetlana; Feldmann, Claus; Konchenko, Sergey N; Roesky, Peter W

2018-05-14

Zintl ions in molecular compounds are of fundamental interest for basic research and application. Two reactive antimony sources are presented that allow direct access to molecular polystibide compounds. These are Sb amalgam (Sb/Hg) and ultrasmall Sb 0 nanoparticles (d=6.6±0.8 nm), which were used independently as precursors for the synthesis of the largest f-element polystibide, [(Cp* 2 Sm) 4 Sb 8 ]. Whereas the reaction of the nanoparticles with [Cp* 2 Sm] directly led to [(Cp* 2 Sm) 4 Sb 8 ], Sm/Sb/Hg intermediates were isolated when using Sb/Hg as the precursor. These Sm/Sb/Hg intermediates [{(Cp* 2 Sm) 2 Sb} 2 (μ-Hg)] and [{(Cp* 2 Sm) 3 (μ 4 ,η 1:2:2:2 -Sb 4 )} 2 Hg] were synthetically trapped and structurally characterized, giving insight in the formation mechanism of polystibide compounds. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Medication Desensitization: Characterization of Outcomes and Risk Factors for Reactions.

Science.gov (United States)

Murray, Taryn S; Rice, Todd W; Wheeler, Arthur P; Phillips, Elizabeth J; Dworski, Ryszard T; Stollings, Joanna L

2016-03-01

Although its mechanisms are poorly understood, desensitization has been used to induce a temporary state of immune unresponsiveness in patients who have IgE-, non-IgE-, or pharmacologically mediated reactions when a drug has no alternatives. The purpose of this study was to characterize the outcomes and identify risk factors for reactions during drug desensitization. A retrospective review of electronic medical records of adult patients undergoing drug desensitization from January 1, 2011, to December 31, 2013, was conducted in 2 intensive care units at a tertiary medical center. We used multivariate analysis to determine if specified risk factors were associated with reacting during the desensitization. Reactions were classified according to the pretest probability prior to desensitization, and then, reactions during desensitization were classified based on the occurrence of cutaneous reactions as follows: successful with no reaction, mild reaction, moderate reaction, or failed. Failure could result from any systemic allergic or cutaneous reaction resulting in procedure termination. The desensitizations were also assessed to determine if the patient required de-escalation secondary to a reaction. A total of 88 desensitizations were performed in 69 patients. Desensitization was completed with no cutaneous reaction in 85% of patients. No baseline characteristic, medication class (P = 0.46), or indication for desensitization (P = 0.59) was associated with having a reaction. Reported histories of urticaria (P desensitization. However, neither history of urticaria nor labored breathing was independently associated with having a reaction in multivariate analysis (OR = 0.979, 95% CI = 0.325-2.952, P = 0.970, and OR = 1.626, 95% CI = 0.536-4.931, P = 0.739, respectively). Drug desensitization is safe for patients who have no alternative for therapy. Reported allergy histories of urticaria and labored breathing are both associated with having a reaction during the

The benzoquinone-mediated electrochemical microbial biosensor for water biotoxicity assay

International Nuclear Information System (INIS)

Li, Jiuming; Yu, Yuan; Wang, Yuning; Qian, Jun; Zhi, Jinfang

2013-01-01

Graphical abstract: The mediator can participate in microorganism respiration, accept the electrons from respiratory chains, and therefore be reduced by microorganism. The re-oxidization currents of mediators on electrode can reflect the microbial activity, and when respiration is suppressed by toxicants, it can be detected by the resulting change of currents. Unlike other biotoxicity tests, which record the toxic effect after a fixed time for incubation of biocomponents and toxicants, this mediated whole cell biosensor can provide a real-time monitor of the microbial activity during the measurement. -- Abstract: A simple mediated microbial biosensor providing real-time monitoring of water quality and evaluation of biotoxicity was fabricated by entrapping Escherichia coli (E. coli) cells in gelatin on glassy carbon electrode with benzoquinone as the redox mediator. The biotoxicity assay was based on the respiratory activity of E. coli cells estimated by the oxidation current of microbially reduced benzoquinone. The neutrality and lipophilicity rendered benzoquinone better efficiency than ferricyanide in mediated microbial reactions. After the optimization of preparation conditions, the prepared microbial biosensors have measured several common toxicants with different concentrations. In addition, the biotoxicity of binary mixtures of heavy metals and wastewater were investigated. The fabricated biosensor exhibited good repeatability and stability in the biotoxicity measurements

Insights into the mechanisms on chemical reactions: reaction paths for chemical reactions

International Nuclear Information System (INIS)

Dunning, T.H. Jr.; Rosen, E.; Eades, R.A.

1987-01-01

We report reaction paths for two prototypical chemical reactions: Li + HF, an electron transfer reaction, and OH + H 2 , an abstraction reaction. In the first reaction we consider the connection between the energetic terms in the reaction path Hamiltonian and the electronic changes which occur upon reaction. In the second reaction we consider the treatment of vibrational effects in chemical reactions in the reaction path formalism. 30 refs., 9 figs

Cucurbit[6]uril p-xylylenediammonium diiodide decahydrate inclusion complex

Directory of Open Access Journals (Sweden)

Wei-Hao Huang

2008-07-01

Full Text Available The title inclusion complex, C36H36N24O12·C8H14N22+·2I−·10H2O, displays a large ellipsoidal deformation of the cucurbit[6]uril (CB[6] skeleton upon complex formation. The benzene ring of the cation is rotationally disordered between two orientations in a ratio of 3:1. The solvent H2O molecules form a hydrogen-bonded network by interaction with the carbonyl groups of CB[6] and the I− counterions. The crystal studied exhibited non-merohedral twinning. Both CB[6] and the cation are centrosymmetric.

Explaining Sex Differences in Reactions to Relationship Infidelities: Comparisons of the Roles of Sex, Gender, Beliefs, Attachment, and Sociosexual Orientation

Directory of Open Access Journals (Sweden)

Gary L. Brase

2014-01-01

Full Text Available To the extent that sex differences are mediated by mechanisms such as sex-roles and beliefs, individual differences in these more proximate traits should account for significant portions of relevant sex differences. Differences between women and men in reactions to sexual and emotional infidelity were assessed in a large sample of participants (n = 477, and these target reactions were evaluated as a function of many potential proximate mediators (infidelity implications beliefs, gender-role beliefs, interpersonal trust, attachment style, sociosexuality, and culture of honor beliefs and as a function of participant sex. Results found a consistent sex difference that was not mediated by any other variables, although a handful of other variables were related to male, but not female, individual differences. These findings suggest particularly promising directions for future research on integrating evolutionarily based sex differences and proximate individual differences.

Explaining sex differences in reactions to relationship infidelities: comparisons of the roles of sex, gender, beliefs, attachment, and sociosexual orientation.

Science.gov (United States)

Brase, Gary L; Adair, Lora; Monk, Kale

2014-02-04

To the extent that sex differences are mediated by mechanisms such as sex-roles and beliefs, individual differences in these more proximate traits should account for significant portions of relevant sex differences. Differences between women and men in reactions to sexual and emotional infidelity were assessed in a large sample of participants (n = 477), and these target reactions were evaluated as a function of many potential proximate mediators (infidelity implications beliefs, gender-role beliefs, interpersonal trust, attachment style, sociosexuality, and culture of honor beliefs) and as a function of participant sex. Results found a consistent sex difference that was not mediated by any other variables, although a handful of other variables were related to male, but not female, individual differences. These findings suggest particularly promising directions for future research on integrating evolutionarily based sex differences and proximate individual differences.

Dynamic pathways to mediate reactions buried in thermal fluctuations. I. Time-dependent normal form theory for multidimensional Langevin equation.

Science.gov (United States)

Kawai, Shinnosuke; Komatsuzaki, Tamiki

2009-12-14

We present a novel theory which enables us to explore the mechanism of reaction selectivity and robust functions in complex systems persisting under thermal fluctuation. The theory constructs a nonlinear coordinate transformation so that the equation of motion for the new reaction coordinate is independent of the other nonreactive coordinates in the presence of thermal fluctuation. In this article we suppose that reacting systems subject to thermal noise are described by a multidimensional Langevin equation without a priori assumption for the form of potential. The reaction coordinate is composed not only of all the coordinates and velocities associated with the system (solute) but also of the random force exerted by the environment (solvent) with friction constants. The sign of the reaction coordinate at any instantaneous moment in the region of a saddle determines the fate of the reaction, i.e., whether the reaction will proceed through to the products or go back to the reactants. By assuming the statistical properties of the random force, one can know a priori a well-defined boundary of the reaction which separates the full position-velocity space in the saddle region into mainly reactive and mainly nonreactive regions even under thermal fluctuation. The analytical expression of the reaction coordinate provides the firm foundation on the mechanism of how and why reaction proceeds in thermal fluctuating environments.

A prospective study of cow milk allergy in Danish infants during the first 3 years of life. Clinical course in relation to clinical and immunological type of hypersensitivity reaction

DEFF Research Database (Denmark)

Høst, A; Halken, S

1990-01-01

A cohort of 1749 newborns from the municipality of Odense born during 1985 at the University Hospital were followed prospectively for the development of IgE-mediated and non-IgE-mediated cow milk allergy (CMA) during their first year. The diagnosis of CMA was based on the results of strict...... elimination/milk challenge procedures in a hospital setting, and continued clinical sensitivity to cow milk (CM) was assessed by rechallenging every 6-12 months until the age of 3 years. Further, in infants with CMA, the clinical course of adverse reactions to other foods and the development of allergy......E-mediated CMA, 19 infants showed "immediate reactions" to CM (within 1 h after intake of 2.3 g milk protein) and 20 infants were "late reactors". No significant correlation between IgE-mediated CMA and "immediate reactions" to CM was demonstrated. The overall prognosis of CMA was good with a total recovery...

Iptycenes with an acridinone motif developed through [4+2] cycloaddition of tethered naphthalene and iminoquinone via a radical reaction.

Science.gov (United States)

Raju, Selvam; Annamalai, Pratheepkumar; Chen, Pei-Ling; Liu, Yi-Hung; Chuang, Shih-Ching

2017-06-06

A new class of iptycenes was developed by combining 2-(naphthalen-1-yl)anilines and p-benzoquinones through copper(ii)-mediated radical cyclisation. This unusual cyclisation reaction resulted in the robust and efficient syntheses of iptycenes with an acridinone motif. These iptycenes can be further transformed into planar acridinone heterocyclics through the Diels-Alder reaction.

Exploration of mild copper-mediated coupling of organotrifluoroborates in the synthesis of thiirane-based inhibitors of matrix metalloproteinases.

Science.gov (United States)

Testero, Sebastian A; Bouley, Renee; Fisher, Jed F; Chang, Mayland; Mobashery, Shahriar

2011-05-01

The copper-mediated and non-basic oxidative cross-coupling of organotrifluoroborates with phenols was applied to elaboration of the structures of thiirane-based inhibitors of matrix metalloproteinases. By revision of the synthetic sequence to allow this cross-coupling as the final step, and taking advantage of the neutral nature of organotrifluoroborate cross-coupling, a focussed series of inhibitors showing aryloxy and alkenyloxy replacement of the phenoxy substituent was prepared. This reaction shows exceptional promise as an alternative to the classic copper-mediated but strongly basic Ullmann reaction, for the diversification of ether segments within base-labile lead structures. Copyright © 2010 Elsevier Ltd. All rights reserved.

Generation of ROS mediated by mechanical waves (ultrasound) and its possible applications.

Science.gov (United States)

Duco, Walter; Grosso, Viviana; Zaccari, Daniel; Soltermann, Arnaldo T

2016-10-15

The thermal decomposition of 9,10 diphenylanthracene peroxide (DPAO 2 ) generates DPA and a mix of triplet and singlet molecular oxygen. For DPAO 2 the efficiency to produce singlet molecular oxygen is 0.35. On the other hand, it has shown that many thermal reactions can be carried out through the interaction of molecules with ultrasound. Ultrasound irradiation can create hydrodynamic stress (sonomechanical process), inertial cavitation (pyrolitic process) and long range effects mediated by radicals or ROS. Sonochemical reactions can be originated by pyrolytic like process, shock mechanical waves, thermal reactions and radical and ROS mediated reactions. Sonolysis of pure water can yield hydrogen or hydroxyl radicals and hydrogen peroxide (ROS). When DPAO 2 in 1,4 dioxane solution is treated with 20 or 24kHz and different power intensity the production of molecular singlet oxygen is observed. Specific scavengers like tetracyclone (TC) are used to demonstrate it. The efficiency now is 0.85 showing that the sonochemical process is much more efficient that the thermal one. Another endoperoxide, artemisinin was also studied. Unlike the concept of photosensitizer of photodynamic therapy, in spite of large amount of reported results in literature, the term sonosensitizer and the sonosensitization process are not well defined. We define sonosensitized reaction as one in which a chemical species decompose as consequence of cavitation phenomena producing ROS or other radicals and some other target species does undergo a chemical reaction. The concept could be reach rapidly other peroxides which are now under experimental studies. For artemisinin, an important antimalarian and anticancer drug, was established that ultrasound irradiation increases the effectiveness of the treatment but without any explanation. We show that artemisinin is an endoperoxide and behaves as a sonosensitizer in the sense of our definition. Copyright © 2016 Elsevier Inc. All rights reserved.

IMMEDIATE REACTIONS TO MONOCLONAL ANTIBODIES IN CLINICAL HEMATOLOGY

Directory of Open Access Journals (Sweden)

Vasiliki KYRIAZI

2016-12-01

Full Text Available Monoclonal antibodies (MoAbs have been widely used in clinical hematology. As foreign macro-molecules, they can cause infusional reactions during the administration or within 24 hours after the infusion, which encompass a spectrum of mechanisms. Although most of these reactions are non-allergic, are often indistinguishable from true allergic reactions mediated by IgE immunoglobulins. The diagnosis is often challenging and relies mainly on clinical criteria. They occur during the first doses, soon after the initiation of treatment. The symptoms are usually well controlled by the immediate drug discontinuation or reduction of the infusion rate. The management remains largely supportive, consisting of oxygen, intravenous fluids, bronchodilators, antihistamines and steroids. Most of MoAb protocols recommend premedication with steroids and antihistamines and gradually escalating infusion rates. Increased medical and nursing vigilance is required and resuscitative equipment should always be readily available. These events affect patients' quality of life, leading to treatment delay or discontinuation and series of tests. The decision to rechallenge the treatment depends on severity grading, clinical parameters and treatment goals. This article provides an update of MoAbs used in clinical hematology. It summarizes the pathophysiology, the diagnostic approach, the preventive measures and treatment of MoAb-related reactions.

Methylene blue as a lignin surrogate in manganese peroxidase reaction systems.

Science.gov (United States)

Goby, Jeffrey D; Penner, Michael H; Lajoie, Curtis A; Kelly, Christine J

2017-11-15

Manganese peroxidase (MnP) is associated with lignin degradation and is thus relevant to lignocellulosic-utilization technologies. Technological applications require reaction mixture optimization. A surrogate substrate can facilitate this if its susceptibility to degradation is easily monitored and mirrors that of lignin. The dye methylene blue (MB) was evaluated in these respects as a surrogate substrate by testing its reactivity in reaction mixtures containing relevant redox mediators (dicarboxylic acids, fatty acids). Relative rates of MB degradation were compared to available literature reports of lignin degradation under similar conditions, and suggest that MB can be a useful lignin surrogate in MnP systems. Copyright © 2017 Elsevier Inc. All rights reserved.

Why Do Lithium-Oxygen Batteries Fail: Parasitic Chemical Reactions and Their Synergistic Effect.

Science.gov (United States)

Yao, Xiahui; Dong, Qi; Cheng, Qingmei; Wang, Dunwei

2016-09-12

As an electrochemical energy-storage technology with the highest theoretical capacity, lithium-oxygen batteries face critical challenges in terms of poor stabilities and low charge/discharge round-trip efficiencies. It is generally recognized that these issues are connected to the parasitic chemical reactions at the anode, electrolyte, and cathode. While the detailed mechanisms of these reactions have been studied separately, the possible synergistic effects between these reactions remain poorly understood. To fill in the knowledge gap, this Minireview examines literature reports on the parasitic chemical reactions and finds the reactive oxygen species a key chemical mediator that participates in or facilitates nearly all parasitic chemical reactions. Given the ubiquitous presence of oxygen in all test cells, this finding is important. It offers new insights into how to stabilize various components of lithium-oxygen batteries for high-performance operations and how to eventually materialize the full potentials of this promising technology. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

sup 8 sup 9 Sr and sup 1 sup 5 sup 3 Sm-EDTMP therapy of disseminated skeletal metastasis

CERN Document Server

Zhang Jun Ning; Zhu Shou Peng

2001-01-01

A retrospective analysis was performed on 72 patients with disseminated skeletal metastasis to evaluate the effect of strontium-89 or samarium-153 EDTMP therapy. There existed 87.88% of clinical response, 12.12% of no response in the group treated with strontium-89 as compared with 90.24% of clinical response, 9.76% no response in one treated with samarium-153 EDTMP; and there were no correlation between the treatment results and the amounts of isotopes administrated. The results suggest that strontium-89 or samarium-153 EDTMP therapy is a method of first choice in the palliative treatment for disseminated skeletal metastasis

89Sr and 153Sm-EDTMP therapy of disseminated skeletal metastasis

International Nuclear Information System (INIS)

Zhang Junning; Hong Chengjiao; Zhu Shoupeng

2001-01-01

A retrospective analysis was performed on 72 patients with disseminated skeletal metastasis to evaluate the effect of strontium-89 or samarium-153 EDTMP therapy. There existed 87.88% of clinical response, 12.12% of no response in the group treated with strontium-89 as compared with 90.24% of clinical response, 9.76% no response in one treated with samarium-153 EDTMP; and there were no correlation between the treatment results and the amounts of isotopes administrated. The results suggest that strontium-89 or samarium-153 EDTMP therapy is a method of first choice in the palliative treatment for disseminated skeletal metastasis

{sup 89}Sr and {sup 153}Sm-EDTMP therapy of disseminated skeletal metastasis

Energy Technology Data Exchange (ETDEWEB)

Junning, Zhang; Chengjiao, Hong; Shoupeng, Zhu [Suzhou Univ., Suzhou (China)

2001-07-01

A retrospective analysis was performed on 72 patients with disseminated skeletal metastasis to evaluate the effect of strontium-89 or samarium-153 EDTMP therapy. There existed 87.88% of clinical response, 12.12% of no response in the group treated with strontium-89 as compared with 90.24% of clinical response, 9.76% no response in one treated with samarium-153 EDTMP; and there were no correlation between the treatment results and the amounts of isotopes administrated. The results suggest that strontium-89 or samarium-153 EDTMP therapy is a method of first choice in the palliative treatment for disseminated skeletal metastasis.

Biomarkers of adverse drug reactions.

Science.gov (United States)

Carr, Daniel F; Pirmohamed, Munir

2018-02-01

Adverse drug reactions can be caused by a wide range of therapeutics. Adverse drug reactions affect many bodily organ systems and vary widely in severity. Milder adverse drug reactions often resolve quickly following withdrawal of the casual drug or sometimes after dose reduction. Some adverse drug reactions are severe and lead to significant organ/tissue injury which can be fatal. Adverse drug reactions also represent a financial burden to both healthcare providers and the pharmaceutical industry. Thus, a number of stakeholders would benefit from development of new, robust biomarkers for the prediction, diagnosis, and prognostication of adverse drug reactions. There has been significant recent progress in identifying predictive genomic biomarkers with the potential to be used in clinical settings to reduce the burden of adverse drug reactions. These have included biomarkers that can be used to alter drug dose (for example, Thiopurine methyltransferase (TPMT) and azathioprine dose) and drug choice. The latter have in particular included human leukocyte antigen (HLA) biomarkers which identify susceptibility to immune-mediated injuries to major organs such as skin, liver, and bone marrow from a variety of drugs. This review covers both the current state of the art with regard to genomic adverse drug reaction biomarkers. We also review circulating biomarkers that have the potential to be used for both diagnosis and prognosis, and have the added advantage of providing mechanistic information. In the future, we will not be relying on single biomarkers (genomic/non-genomic), but on multiple biomarker panels, integrated through the application of different omics technologies, which will provide information on predisposition, early diagnosis, prognosis, and mechanisms. Impact statement • Genetic and circulating biomarkers present significant opportunities to personalize patient therapy to minimize the risk of adverse drug reactions. ADRs are a significant heath issue

Role of Mast Cells in Oral Lichen Planus and Oral Lichenoid Reactions.

Science.gov (United States)

Ramalingam, Suganya; Malathi, Narasimhan; Thamizhchelvan, Harikrishnan; Sangeetha, Narasimhan; Rajan, Sharada T

2018-01-01

Oral lichen planus (OLP) is a chronic T cell mediated disease of oral mucosa, skin, and its appendages with a prevalence of 0.5 to 2.6% worldwide. Oral lichenoid reactions (OLR) are a group of lesions with diverse aetiologies but have clinical and histological features similar to OLP, thereby posing a great challenge in differentiating both lesions. Mast cells are multifunctional immune cells that play a major role in the pathogenesis of lichen planus by release of certain chemical mediators. Increased mast cell densities with significant percentage of degranulation have been observed as a consistent finding in pathogenesis of oral lichen planus. The current study was aimed at quantifying the mast cells in histopathological sections of OLP and OLR thereby aiding a means of distinguishing these lesions. The study group involved 21 cases of oral lichen planus, 21 cases of oral lichenoid reactions, and 10 control specimens of normal buccal mucosa. All the cases were stained with Toluidine Blue and routine haematoxylin and eosin and the mast cells were quantified. The results were analyzed using the Kruskal-Wallis test and an intergroup analysis was performed using Mann-Whitney U test. The number of mast cells showed an increased value in oral lichen planus when compared to oral lichenoid reaction and thus an estimation of mast cells count could aid in distinguishing OLP from OLR histopathologically.

Mediation Analysis with Multiple Mediators

OpenAIRE

VanderWeele, T.J.; Vansteelandt, S.

2014-01-01

Recent advances in the causal inference literature on mediation have extended traditional approaches to direct and indirect effects to settings that allow for interactions and non-linearities. In this paper, these approaches from causal inference are further extended to settings in which multiple mediators may be of interest. Two analytic approaches, one based on regression and one based on weighting are proposed to estimate the effect mediated through multiple mediators and the effects throu...

ABTS-Modified Silica Nanoparticles as Laccase Mediators for Decolorization of Indigo Carmine Dye

Directory of Open Access Journals (Sweden)

Youxun Liu

2015-01-01

Full Text Available Efficient reuse and regeneration of spent mediators are highly desired for many of the laccases’ biotechnology applications. This investigation demonstrates that a redox mediator 2,2′-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid (ABTS covalently attached to silica nanoparticles (SNPs effectively mediated dye decolorization catalyzed by laccase. Characteristics of ABTS-modified silica nanoparticles (ABTS-SNPs were researched by scanning electron microscopy and Fourier-transformed infrared spectroscopy. When ABTS and ABTS-SNPs were used as laccase mediators, the decolorization yields of 96 and 95% were, respectively, obtained for indigo carmine dye. The results suggest that ABTS immobilized on SNPs can be used as laccase mediators as they retain almost the same efficiency as the free ABTS. The oxidized ABTS-SNPs were regenerated by their reduction reaction with ascorbic acid. Decolorization efficiency of regenerated ABTS-SNPs and their initial forms were found to be almost equivalent. Six reuse cycles for spent ABTS-SNPs were run for the treatment of indigo carmine, providing decolorization yields of 96–77%. Compared with free mediator, the immobilized mediators have the advantage of being easily recovered, regenerated, and reused making the whole process environmentally friendly.

A study for characterization of IgE-mediated cutaneous immediate and late-phase reactions in non-allergic domestic cats.

Science.gov (United States)

Seals, Shanna L; Kearney, Michael; Del Piero, Fabio; Hammerberg, Bruce; Pucheu-Haston, Cherie M

2014-05-15

Immunoglobulin-E (IgE) mediated reactions can be induced by intradermal injection of anti-IgE antibodies in both humans and dogs. These reactions grossly and histologically mimic changes seen in naturally occurring allergic dermatitis in these species. Similar studies have not been conducted in the cat. Purified polyclonal rabbit-origin IgG specific for canine IgE (anti-IgE) and rabbit immunoglobulin G (IgG) were injected intradermally in 7 non-allergic laboratory colony cats. Wheal measurements were obtained and biopsies collected before injection and at injection sites after 20 min, 6, 24, and 48 h. Injection of anti-IgE induced an immediate wheal response which was significantly larger than that seen after injection of rabbit IgG. Anti-IgE injected skin was also significantly thicker than IgG-injected skin. This corresponded with a significant increase in number of visibly degranulated mast cells in anti-IgE samples when compared to IgG samples. Injection of anti-IgE was associated with the rapid recruitment of inflammatory cells to the injected dermis. The number of inflammatory cells and mononuclear cells were significantly elevated after the injection of anti-IgE when compared to IgG-injected skin. Both eosinophils and neutrophils were significantly increased in anti-IgE samples relative to IgG, although neutrophils were only transiently increased. The high eosinophil and relatively low neutrophil cell counts in these samples were consistent with previously documented histologic features of naturally occurring feline allergic skin disease. Immunohistochemistry identified a significantly overall increased CD1a(+) cells after the intradermal injection of anti-IgE when compared to IgG and non-injected skin. CD3(+), CD8(+) and CD4(+) were also significantly increased overall in anti-IgE injected skin relative to IgG injected skin. These data document the gross and cellular response to injection of anti-IgE in the skin of healthy, non-allergic cats and support a

Assay for Human Rad51-Mediated DNA Displacement Loop Formation

OpenAIRE

sprotocols

2014-01-01

Authors: Steven Raynard and Patrick Sung Corresponding author ([]()) ### INTRODUCTION Homologous recombination is an important mechanism for the repair of damaged chromosomes, for preventing the demise of damaged replication forks, and for several other aspects of chromosome metabolism and maintenance. The homologous recombination reaction is mediated by the Rad51 recombinase. In the presence of ATP, Rad51 polymerizes on single-stranded D...

Leprosy reactions in postelimination stage: the Bangladesh experience.

Science.gov (United States)

Mowla, M R; Ara, S; Mizanur Rahman, A F M; Tripura, S P; Paul, S

2017-04-01

Leprosy reactions are immunologically mediated conditions and a major cause of disability before, during and after multidrug therapy (MDT). Little data have been published on the epidemiology of leprosy reactions in Bangladesh. To describe the pattern and prevalence of leprosy reactions in the postelimination stage. A descriptive retrospective cross-sectional study was carried out in Chittagong Medical College Hospital using the registered records of patients in the period between 2004 and 2013. Of the 670 patients with leprosy, 488 (73.38%) were males and 182 (27.37%) were females. The prevalence of reaction was in 300 (44.78%) patients with a male:female ratio of 3.55 : 1. The age-specific cumulative reaction cases at >40 years were 115 (38.33%) among all age groups. The prevalence of reaction was found to be in 166 (55.33%) patients for the reversal reaction, 49 (16.57%) for the erythema nodosum leprosum (ENL) and 85 (28.33%) for the neuritis. Borderline tuberculoid was most common (106, 35.33%)in the reversal reaction group, while lepromatous leprosy was most common (37, 12.33%) in ENL group. More than half of the patients (169, 56.33%) had reactions at the time of presentations, while 85 (28.33%) and 46 (15.33%) patients developed reaction during and after MDT, respectively. The reversal reaction group presented with ≥six skin lesions in 96 (57.83%) patients and ≥two nerve function impairments (NFIs) in 107 (64.46%) patients. The ENL was present chiefly as papulo-nodular lesions in 45 (91.84%) patients followed by pustule-necrotic lesions in four (8.16%), neuritis in 33 (67.35%), fever in 24 (48.98%), lymphadenitis in six (12.24%), arthritis in five (10.20%) and iritis in two (4.08%). Bacterial index ≥3 had been demonstrated in 34 (60.71%) patients in ENL group. The incidence of leprosy reaction seemed to be more than three times common in borderline tuberculoid (52.33%) group than in lepromatous leprosy (14%) group. Reactions with NFI and disability

P(NMe2)3-Mediated Umpolung Alkylation and Nonylidic Olefination of α-Keto Esters.

Science.gov (United States)

Wang, Sunewang Rixin; Radosevich, Alexander T

2015-08-07

A commercial phosphorus-based reagent (P(NMe2)3) mediates umpolung alkylation of methyl aroylformates with benzylic and allylic bromides, leading to either Barbier-type addition or ylide-free olefination products upon workup. The reaction sequence is initiated by a two-electron redox addition of the tricoordinate phosphorus reagent with an α-keto ester compound (Kukhtin-Ramirez addition). A mechanistic rationale is offered for the chemoselectivity upon which the success of this nonmetal mediated C-C bond forming strategy is based.

Cyclisation versus 1,1-Carboboration: Reactions of B(C6F5)3 with Propargyl Amides.

Science.gov (United States)

Melen, Rebecca L; Hansmann, Max M; Lough, Alan J; Hashmi, A Stephen K; Stephan, Douglas W

2013-09-02

A series of propargyl amides were prepared and their reactions with the Lewis acidic compound B(C6F5)3 were investigated. These reactions were shown to afford novel heterocycles under mild conditions. The reaction of a variety of N-substituted propargyl amides with B(C6F5)3 led to an intramolecular oxo-boration cyclisation reaction, which afforded the 5-alkylidene-4,5-dihydrooxazolium borate species. Secondary propargyl amides gave oxazoles in B(C6F5)3 mediated (catalytic) cyclisation reactions. In the special case of disubstitution adjacent to the nitrogen atom, 1,1-carboboration is favoured as a result of the increased steric hindrance (1,3-allylic strain) in the 5-alkylidene-4,5-dihydrooxazolium borate species. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

IgE-mediated chlorhexidine allergy: a new occupational hazard?

DEFF Research Database (Denmark)

Nagendran, Vasantha; Wicking, Jennifer; Ekbote, Anjali

2009-01-01

BACKGROUND: Chlorhexidine is an effective antimicrobial agent commonly used in UK hospitals, primarily for skin decontamination. Recent UK infection control guidelines recommend the use of 2% chlorhexidine solution in specific clinical settings, thus increasing chlorhexidine use by health care...... those with possible clinical allergy to come forward for further testing. Diagnosis was based on an appropriate clinical history with positive serum-specific IgE to chlorhexidine and/or positive skin prick testing. RESULTS: Four cases of occupational IgE-mediated allergy to chlorhexidine were identified...... workers (HCWs). Chlorhexidine has been widely reported to cause IgE-mediated allergic reactions (from urticaria and angioedema to anaphylaxis) among patients undergoing surgery/invasive procedures. Despite its widespread use in health care settings, there are no reports of clinically confirmed...

Determining Li+-Coupled Redox Targeting Reaction Kinetics of Battery Materials with Scanning Electrochemical Microscopy.

Science.gov (United States)

Yan, Ruiting; Ghilane, Jalal; Phuah, Kia Chai; Pham Truong, Thuan Nguyen; Adams, Stefan; Randriamahazaka, Hyacinthe; Wang, Qing

2018-02-01

The redox targeting reaction of Li + -storage materials with redox mediators is the key process in redox flow lithium batteries, a promising technology for next-generation large-scale energy storage. The kinetics of the Li + -coupled heterogeneous charge transfer between the energy storage material and redox mediator dictates the performance of the device, while as a new type of charge transfer process it has been rarely studied. Here, scanning electrochemical microscopy (SECM) was employed for the first time to determine the interfacial charge transfer kinetics of LiFePO 4 /FePO 4 upon delithiation and lithiation by a pair of redox shuttle molecules FcBr 2 + and Fc. The effective rate constant k eff was determined to be around 3.70-6.57 × 10 -3 cm/s for the two-way pseudo-first-order reactions, which feature a linear dependence on the composition of LiFePO 4 , validating the kinetic process of interfacial charge transfer rather than bulk solid diffusion. In addition, in conjunction with chronoamperometry measurement, the SECM study disproves the conventional "shrinking-core" model for the delithiation of LiFePO 4 and presents an intriguing way of probing the phase boundary propagations induced by interfacial redox reactions. This study demonstrates a reliable method for the kinetics of redox targeting reactions, and the results provide useful guidance for the optimization of redox targeting systems for large-scale energy storage.

Utilization of corn cob biochar in a direct carbon fuel cell

Science.gov (United States)

Yu, Jinshuai; Zhao, Yicheng; Li, Yongdan

2014-12-01

Biochar obtained from the pyrolysis of corn cob is used as the fuel of a direct carbon fuel cell (DCFC) employing a composite electrolyte composed of a samarium doped ceria (SDC) and a eutectic carbonate phase. An anode layer made of NiO and SDC is utilized to suppress the cathode corrosion by the molten carbonate and improves the whole cell stability. The anode off-gas of the fuel cell is analyzed with a gas chromatograph. The effect of working temperature on the cell resistance and power output is examined. The maximum power output achieves 185 mW cm-2 at a current density of 340 mA cm-2 and 750 °C. An anode reaction scheme including the Boudouard reaction is proposed.

Chloride (Cl−) ion-mediated shape control of palladium nanoparticles

International Nuclear Information System (INIS)

Nalajala, Naresh; Chakraborty, Arup; Bera, Bapi; Neergat, Manoj

2016-01-01

The shape control of Pd nanoparticles is investigated using chloride (Cl − ) ions as capping agents in an aqueous medium in the temperature range of 60–100 °C. With weakly adsorbing and strongly etching Cl − ions, oxygen plays a crucial role in shape control. The experimental factors considered are the concentration of the capping agents, reaction time and reaction atmosphere. Thus, Pd nanoparticles of various shapes with high selectivity can be synthesized. Moreover, the removal of Cl − ions from the nanoparticle surface is easier than that of Br − ions (moderately adsorbing and etching) and I − ions (strongly adsorbing and weakly etching). The cleaned Cl − ion-mediated shape-controlled Pd nanoparticles are electrochemically characterized and the order of the half-wave potential of the oxygen reduction reaction in oxygen-saturated 0.1 M HClO 4 solution is of the same order as that observed with single-crystal Pd surfaces. (paper)

Water-mediated electrochemical nano-writing on thin ceria films

International Nuclear Information System (INIS)

Yang, Nan; Doria, Sandra; Tebano, Antonello; Licoccia, Silvia; Balestrino, Giuseppe; Kumar, Amit; Arruda, Thomas M; Jesse, Stephen; Ivanov, Ilia N; Baddorf, Arthur P; Strelcov, Evgheni; Kalinin, Sergei V; Jang, Jae Hyuck; Borisevich, Albina Y

2014-01-01

Bias dependent mechanisms of irreversible cathodic and anodic processes on a pure CeO 2 film are studied using modified atomic force microscopy (AFM). For a moderate positive bias applied to the AFM tip an irreversible electrochemical reduction reaction is found, associated with significant local volume expansion. By changing the experimental conditions we are able to deduce the possible role of water in this process. Simultaneous detection of tip height and current allows the onset of conductivity and the electrochemical charge transfer process to be separated, further elucidating the reaction mechanism. The standard anodic/cathodic behavior is recovered in the high bias regime, where a sizable transport current flows between the tip and the film. These studies give insight into the mechanisms of the tip-induced electrochemical reactions as mediated by electronic currents, and into the role of water in these processes, as well as providing a different approach for electrochemical nano-writing. (paper)

Mediation analysis with time varying exposures and mediators.

Science.gov (United States)

VanderWeele, Tyler J; Tchetgen Tchetgen, Eric J

2017-06-01

In this paper we consider causal mediation analysis when exposures and mediators vary over time. We give non-parametric identification results, discuss parametric implementation, and also provide a weighting approach to direct and indirect effects based on combining the results of two marginal structural models. We also discuss how our results give rise to a causal interpretation of the effect estimates produced from longitudinal structural equation models. When there are time-varying confounders affected by prior exposure and mediator, natural direct and indirect effects are not identified. However, we define a randomized interventional analogue of natural direct and indirect effects that are identified in this setting. The formula that identifies these effects we refer to as the "mediational g-formula." When there is no mediation, the mediational g-formula reduces to Robins' regular g-formula for longitudinal data. When there are no time-varying confounders affected by prior exposure and mediator values, then the mediational g-formula reduces to a longitudinal version of Pearl's mediation formula. However, the mediational g-formula itself can accommodate both mediation and time-varying confounders and constitutes a general approach to mediation analysis with time-varying exposures and mediators.

o-Iodoxybenzoic acid mediated oxidative desulfurization initiated domino reactions for synthesis of azoles.

Science.gov (United States)

Chaudhari, Pramod S; Pathare, Sagar P; Akamanchi, Krishnacharaya G

2012-04-20

A systematic exploration of thiophilic ability of o-iodoxybenzoic acid (IBX) for oxidative desulfurization to trigger domino reactions leading to new methodologies for synthesis of different azoles is described. A variety of highly substituted oxadiazoles, thiadiazoles, triazoles, and tetrazoles have been successfully synthesized in good to excellent yields, starting from readily accessible thiosemicarbazides, bis-diarylthiourea, 1,3-disubtituted thiourea, and thioamides. © 2012 American Chemical Society

¹⁹F magnetic resonance probes for live-cell detection of peroxynitrite using an oxidative decarbonylation reaction.

Science.gov (United States)

Bruemmer, Kevin J; Merrikhihaghi, Sara; Lollar, Christina T; Morris, Siti Nur Sarah; Bauer, Johannes H; Lippert, Alexander R

2014-10-21

We report a newly discovered oxidative decarbonylation reaction of isatins that is selectively mediated by peroxynitrite (ONOO(-)) to provide anthranilic acid derivatives. We have harnessed this rapid and selective transformation to develop two reaction-based probes, 5-fluoroisatin and 6-fluoroisatin, for the low-background readout of ONOO(-) using (19)F magnetic resonance spectroscopy. 5-fluoroisatin was used to non-invasively detect ONOO(-) formation in living lung epithelial cells stimulated with interferon-γ (IFN-γ).

Organocatalyzed, Visible-Light Photoredox-Mediated, One-Pot Minisci Reaction Using Carboxylic Acids via N-(Acyloxy)phthalimides.

Science.gov (United States)

Sherwood, Trevor C; Li, Ning; Yazdani, Aliza N; Dhar, T G Murali

2018-03-02

An improved, one-pot Minisci reaction has been developed using visible light, an organic photocatalyst, and carboxylic acids as radical precursors via the intermediacy of in situ-generated N-(acyloxy)phthalimides. The conditions employed are mild, demonstrate a high degree of functional group tolerance, and do not require a large excess of the carboxylic acid reactant. As a result, this reaction can be applied to drug-like scaffolds and molecules with sensitive functional groups, enabling late-stage functionalization, which is of high interest to medicinal chemistry.

Emotional and behavioral reactions to facially deformed patients before and after craniofacial surgery.

Science.gov (United States)

Barden, R C; Ford, M E; Wilhelm, W M; Rogers-Salyer, M; Salyer, K E

1988-09-01

The present experiment investigated whether observers' emotional and behavioral reactions to facially deformed patients could be substantially improved by surgical procedures conducted by well-trained specialists in an experienced multidisciplinary team. Also investigated was the hypothesis that emotional states mediate the effects of physical attractiveness and facial deformity on social interaction. Twenty patients between the ages of 3 months and 17 years were randomly selected from over 2000 patients' files of Kenneth E. Salyer of Dallas, Texas. Patient diagnoses included facial clefts, hypertelorism, Treacher Collins syndrome, and craniofacial dysostoses (Crouzon's and Apert's syndromes). Rigorously standardized photographs of patients taken before and after surgery were shown to 22 "naive" raters ranging in age from 18 to 54 years. Raters were asked to predict their emotional and behavioral responses to the patients. These ratings indicated that observers' behavioral reactions to facially deformed children and adolescents would be more positive following craniofacial surgery. Similarly, the ratings indicated that observers' emotional reactions to these patients would be more positive following surgery. The results are discussed in terms of current sociopsychologic theoretical models for the effects of attractiveness on social interaction. A new model is presented that implicates induced emotional states as a mediating process in explaining the effects of attractiveness and facial deformity on the quality of social interactions. Limitations of the current investigation and directions for future research are also discussed.

Photodegradable, Photoadaptable Hydrogels via Radical-Mediated Disulfide Fragmentation Reaction.

Science.gov (United States)

Fairbanks, Benjamin D; Singh, Samir P; Bowman, Christopher N; Anseth, Kristi S

2011-04-26

Various techniques have been adopted to impart a biological responsiveness to synthetic hydrogels for the delivery of therapeutic agents as well as the study and manipulation of biological processes and tissue development. Such techniques and materials include polyelectrolyte gels that swell and deswell with changes in pH, thermosensitive gels that contract at physiological temperatures, and peptide cross-linked hydrogels that degrade upon peptidolysis by cell-secreted enzymes. Herein we report a unique approach to photochemically deform and degrade disulfide cross-linked hydrogels, mitigating the challenges of light attenuation and low quantum yield, permitting the degradation of hydrogels up to 2 mm thick within 120 s at low light intensities (10 mW/cm(2) at 365 nm). Hydrogels were formed by the oxidation of thiol-functionalized 4-armed poly(ethylene glycol) macromolecules. These disulfide cross-linked hydrogels were then swollen in a lithium acylphosphinate photoinitiator solution. Upon exposure to light, photogenerated radicals initiate multiple fragmentation and disulfide exchange reactions, permitting and promoting photodeformation, photowelding, and photodegradation. This novel, but simple, approach to generate photoadaptable hydrogels portends the study of cellular response to mechanically and topographically dynamic substrates as well as novel encapsulations by the welding of solid substrates. The principles and techniques described herein hold implications for more than hydrogel materials but also for photoadaptable polymers more generally.

Key Building Blocks via Enzyme-Mediated Synthesis

Science.gov (United States)

Fischer, Thomas; Pietruszka, Jörg

Biocatalytic approaches to valuable building blocks in organic synthesis have emerged as an important tool in the last few years. While first applications were mainly based on hydrolases, other enzyme classes such as oxidoreductases or lyases moved into the focus of research. Nowadays, a vast number of biotransformations can be found in the chemical and pharmaceutical industries delivering fine chemicals or drugs. The mild reaction conditions, high stereo-, regio-, and chemoselectivities, and the often shortened reaction pathways lead to economical and ecological advantages of enzymatic conversions. Due to the enormous number of enzyme-mediated syntheses, the present chapter is not meant to be a complete review, but to deliver comprehensive insights into well established enzymatic systems and recent advances in the application of enzymes in natural product synthesis. Furthermore, it is focused on the most frequently used enzymes or enzyme classes not covered elsewhere in the present volume.

The association between choice stepping reaction time and falls in older adults--a path analysis model

NARCIS (Netherlands)

Pijnappels, M.A.G.M.; Delbaere, K.; Sturnieks, D.L.; Lord, S.R.

2010-01-01

Background: choice stepping reaction time (CSRT) is a functional measure that has been shown to significantly discriminate older fallers from non-fallers. Objective: to investigate how physiological and cognitive factors mediate the association between CSRT performance and multiple falls by use of

The chemical foundations of nitroalkene fatty acid signaling through addition reactions with thiols.

Science.gov (United States)

Turell, Lucía; Steglich, Martina; Alvarez, Beatriz

2018-03-22

Nitroalkene fatty acids can be formed in vivo and administered exogenously. They exert pleiotropic signaling actions with cytoprotective and antiinflammatory effects. The presence of the potent electron withdrawing nitro group confers electrophilicity to the adjacent β-carbon. Thiols (precisely, thiolates) are strong nucleophiles and can react with nitroalkene fatty acids through reversible Michael addition reactions. In addition, nitroalkene fatty acids can undergo several other processes including metabolic oxidation, reduction, esterification, nitric oxide release and partition into hydrophobic compartments. The signaling actions of nitroalkenes are mainly mediated by reactions with critical thiols in regulatory proteins. Thus, the thio-Michael addition reaction provides a framework for understanding the molecular basis of the biological effects of nitroalkene fatty acids at the crossroads of thiol signaling and electrophilic lipid signaling. In this review, we describe the reactions of nitroalkene fatty acids in biological contexts. We focus on the Michael addition-elimination reaction with thiols and its mechanism, and extrapolate kinetic and thermodynamic considerations to in vivo settings. Copyright © 2018 Elsevier Inc. All rights reserved.

Highly Diastereoselective Indium-Mediated Allylation of Proline-Derived Hydrazones

International Nuclear Information System (INIS)

Satyender, Apuri; Jang, Doo Ok

2013-01-01

A highly diastereoselective indium-mediated addition reaction to L-proline-derived hydrazones has been developed. The method affords an efficient and general synthesis of homoallylic amines of high optically purity in high yields and diastereomeric ratios up to 98:2. It is well known that (S)-1-amino-2-methoxymethylpyrro-lidine and (S)-4-isopropyl- or (S)-4-phenylmethyl-oxa-zolidin-2-one-derived hydrazones have been used for metal-mediated diastereoselective allylation additions to produce chiral homoallylic amines. However, the optically pure hydrazine precursors are either commercially expensive and/or involve laborious synthetic procedures employing toxic reagents for their preparation. Thus, the design of novel classes of chiral hydrazines that would further broaden the scope of asymmetric synthesis to access optically pure homoallylic amines is highly desirable

Zinc mediated activation of terminal alkynes: stereoselective synthesis of alkynyl glycosides.

Science.gov (United States)

Tatina, Madhu Babu; Kusunuru, Anil Kumar; Yousuf, Syed Khalid; Mukherjee, Debaraj

2014-10-28

Zinc mediated alkynylation reaction was studied for the preparation of C-glycosides from unactivated alkynes. Different glycosyl donors such as glycals and anomeric acetates were tested towards an alkynyl zinc reagent obtained from alkynes using zinc dust and ethyl bromoacetate as an additive. The method provides simple, mild and stereoselective access to alkynyl glycosides both from aromatic and aliphatic acetylenes.

Interventional Effects for Mediation Analysis with Multiple Mediators.

Science.gov (United States)

Vansteelandt, Stijn; Daniel, Rhian M

2017-03-01

The mediation formula for the identification of natural (in)direct effects has facilitated mediation analyses that better respect the nature of the data, with greater consideration of the need for confounding control. The default assumptions on which it relies are strong, however. In particular, they are known to be violated when confounders of the mediator-outcome association are affected by the exposure. This complicates extensions of counterfactual-based mediation analysis to settings that involve repeatedly measured mediators, or multiple correlated mediators. VanderWeele, Vansteelandt, and Robins introduced so-called interventional (in)direct effects. These can be identified under much weaker conditions than natural (in)direct effects, but have the drawback of not adding up to the total effect. In this article, we adapt their proposal to achieve an exact decomposition of the total effect, and extend it to the multiple mediator setting. Interestingly, the proposed effects capture the path-specific effects of an exposure on an outcome that are mediated by distinct mediators, even when-as often-the structural dependence between the multiple mediators is unknown, for instance, when the direction of the causal effects between the mediators is unknown, or there may be unmeasured common causes of the mediators.

A marine microbial consortium apparently mediating anaerobic oxidation of methane

DEFF Research Database (Denmark)

Boetius, A.; Ravenschlag, K.; Schubert, CJ

2000-01-01

microorganisms mediating this reaction have not yet been isolated, and the pathway of anaerobic oxidation of methane is insufficiently understood. Recent data suggest that certain archaea reverse the process of methanogenesis by interaction with sulphate-reducing bacteria(5-7). Here we provide microscopic...... cells and are surrounded by sulphate-reducing bacteria. These aggregates were abundant in gas-hydrate-rich sediments with extremely high rates of methane-based sulphate reduction, and apparently mediate anaerobic oxidation of methane.......A large fraction of globally produced methane is converted to CO2 by anaerobic oxidation in marine sediments(1). Strong geochemical evidence for net methane consumption in anoxic sediments is based on methane profiles(2), radiotracer experiments(3) and stable carbon isotope data(4). But the elusive...

Opening a Can of Worms: Leprosy Reactions and Complicit Soil-Transmitted Helminths.

Science.gov (United States)

Hagge, Deanna A; Parajuli, Pawan; Kunwar, Chhatra B; Rana, Divya R S J B; Thapa, Ruby; Neupane, Kapil D; Nicholls, Peter; Adams, Linda B; Geluk, Annemieke; Shah, Mahesh; Napit, Indra B

2017-09-01

>94% of new annual leprosy cases are diagnosed in populations co-endemic for soil-transmitted helminths (STH). STH can profoundly dysregulate host immune responses towards Th2 bias, which can be restored over time after deworming. We hypothesize that STH co-infection is associated with leprosy reaction (denoted as simply "reaction" herein) occurrence within a co-endemic population. A cohort study was performed on a cohort of Nepalese leprosy patients across treatment and diagnostic classifications who were screened by routine fecal smear microscopy and multiplex quantitative PCR (qPCR) for Ascaris lumbricoides (Al), Strongyloides stercoralis (Ss), Ancyclostoma duodenale (Ad) and Necator americanus (Na). Among 145 patients, 55% were positive for ≥1 STH (STH+): 34% Al+, 18% Ss+, 17% Ad+and 5% Na+. Significant inverse STH and reaction relationships were evidenced by the bulk of cases: 63% reaction-negative were STH+ of total cases (p=0.030) while 65% reaction-positive were STH- in new cases (96; p=0.023). Strikingly, the majority of STH+ were reaction-negative, even when considering each species: 59% Al+, 60% Ss+, 62% Ad+and 67% Na+of new leprosy cases. Absence of STH co-infection is associated with leprosy reaction at diagnosis within a co-endemic population. This is likely due to immune reconstitution effects after deworming or interruption of chronic STH-mediated immune dysregulation. Copyright © 2017. Published by Elsevier B.V.

Diels-Alder Reaction of Isobenzofurans/Cyclopentadienones with Tetrathiafulvalene: Preparation of Naphthalene, Fluoranthene, and Fluorenone Derivatives.

Science.gov (United States)

Karunakaran, Jayachandran; Mohanakrishnan, Arasambattu K

2018-02-16

Diels-Alder reaction of 1,3-diarylbenzo[c]furan/cyclopentadienone with TTF followed by triflic acid mediated cleavage of the resulting adducts led to the formation of the respective 1,4-diaryl substituted naphthalenes, fluoranthenes, and fluorenones. The photophysical properties of representative diaryl-substituted hydrocarbons are also reported.

N-Heterocyclic-Carbene-Catalysed Diastereoselective Vinylogous Mukaiyama/Michael Reaction of 2-(Trimethylsilyloxy)furan and Enones

KAUST Repository

Wang, Ying; Du, Guang Fen; Xing, Fen; Huang, Kuo-Wei; Dai, Bin; He, Lin

2015-01-01

N-heterocyclic carbenes have been utilised as highly efficient nucleophilic organocatalysts to mediate vinylogous Mukaiyama/Michael reactions of 2-(trimethylsilyloxy)furan with enones to afford γ-substituted butenolides in 44-99% yield with 3:1-32:1 diastereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

N-Heterocyclic-Carbene-Catalysed Diastereoselective Vinylogous Mukaiyama/Michael Reaction of 2-(Trimethylsilyloxy)furan and Enones

KAUST Repository

Wang, Ying

2015-10-15

N-heterocyclic carbenes have been utilised as highly efficient nucleophilic organocatalysts to mediate vinylogous Mukaiyama/Michael reactions of 2-(trimethylsilyloxy)furan with enones to afford γ-substituted butenolides in 44-99% yield with 3:1-32:1 diastereoselectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Estimation of causal mediation effects for a dichotomous outcome in multiple-mediator models using the mediation formula.

Science.gov (United States)

Wang, Wei; Nelson, Suchitra; Albert, Jeffrey M

2013-10-30

Mediators are intermediate variables in the causal pathway between an exposure and an outcome. Mediation analysis investigates the extent to which exposure effects occur through these variables, thus revealing causal mechanisms. In this paper, we consider the estimation of the mediation effect when the outcome is binary and multiple mediators of different types exist. We give a precise definition of the total mediation effect as well as decomposed mediation effects through individual or sets of mediators using the potential outcomes framework. We formulate a model of joint distribution (probit-normal) using continuous latent variables for any binary mediators to account for correlations among multiple mediators. A mediation formula approach is proposed to estimate the total mediation effect and decomposed mediation effects based on this parametric model. Estimation of mediation effects through individual or subsets of mediators requires an assumption involving the joint distribution of multiple counterfactuals. We conduct a simulation study that demonstrates low bias of mediation effect estimators for two-mediator models with various combinations of mediator types. The results also show that the power to detect a nonzero total mediation effect increases as the correlation coefficient between two mediators increases, whereas power for individual mediation effects reaches a maximum when the mediators are uncorrelated. We illustrate our approach by applying it to a retrospective cohort study of dental caries in adolescents with low and high socioeconomic status. Sensitivity analysis is performed to assess the robustness of conclusions regarding mediation effects when the assumption of no unmeasured mediator-outcome confounders is violated. Copyright © 2013 John Wiley & Sons, Ltd.

Estimation of Causal Mediation Effects for a Dichotomous Outcome in Multiple-Mediator Models using the Mediation Formula

Science.gov (United States)

Nelson, Suchitra; Albert, Jeffrey M.

2013-01-01

Mediators are intermediate variables in the causal pathway between an exposure and an outcome. Mediation analysis investigates the extent to which exposure effects occur through these variables, thus revealing causal mechanisms. In this paper, we consider the estimation of the mediation effect when the outcome is binary and multiple mediators of different types exist. We give a precise definition of the total mediation effect as well as decomposed mediation effects through individual or sets of mediators using the potential outcomes framework. We formulate a model of joint distribution (probit-normal) using continuous latent variables for any binary mediators to account for correlations among multiple mediators. A mediation formula approach is proposed to estimate the total mediation effect and decomposed mediation effects based on this parametric model. Estimation of mediation effects through individual or subsets of mediators requires an assumption involving the joint distribution of multiple counterfactuals. We conduct a simulation study that demonstrates low bias of mediation effect estimators for two-mediator models with various combinations of mediator types. The results also show that the power to detect a non-zero total mediation effect increases as the correlation coefficient between two mediators increases, while power for individual mediation effects reaches a maximum when the mediators are uncorrelated. We illustrate our approach by applying it to a retrospective cohort study of dental caries in adolescents with low and high socioeconomic status. Sensitivity analysis is performed to assess the robustness of conclusions regarding mediation effects when the assumption of no unmeasured mediator-outcome confounders is violated. PMID:23650048

Iodine-Mediated Intramolecular Dehydrogenative Coupling: Synthesis of N-Alkylindolo[3,2-c]- and -[2,3-c]quinoline Iodides.

Science.gov (United States)

Volvoikar, Prajesh S; Tilve, Santosh G

2016-03-04

An I2/TBHP-mediated intramolecular dehydrogenative coupling reaction is developed for the synthesis of a library of medicinally important 5,11-dialkylindolo[3,2-c]quinoline salts and 5,7-dimethylindolo[2,3-c]quinoline salts. The annulation reaction is followed by aromatization to yield tetracycles in good yield. This protocol is also demonstrated for the synthesis of the naturally occurring isocryptolepine in salt form.

Interfacial Mechanism in Lithium-Sulfur Batteries: How Salts Mediate the Structure Evolution and Dynamics.

Science.gov (United States)

Lang, Shuang-Yan; Xiao, Rui-Juan; Gu, Lin; Guo, Yu-Guo; Wen, Rui; Wan, Li-Jun

2018-06-08

Lithium-sulfur batteries possess favorable potential for energy-storage applications due to their high specific capacity and the low cost of sulfur. Intensive understanding of the interfacial mechanism, especially the polysulfide formation and transformation under complex electrochemical environment, is crucial for the build-up of advanced batteries. Here we report the direct visualization of interfacial evolution and dynamic transformation of the sulfides mediated by the lithium salts via real-time atomic force microscopy monitoring inside a working battery. The observations indicate that the lithium salts influence the structures and processes of sulfide deposition/decomposition during discharge/charge. Moreover, the distinct ion interaction and diffusion in electrolytes manipulate the interfacial reactions determining the kinetics of the sulfide transformation. Our findings provide deep insights into surface dynamics of lithium-sulfur reactions revealing the salt-mediated mechanisms at nanoscale, which contribute to the profound understanding of the interfacial processes for the optimized design of lithium-sulfur batteries.

Facile reactions of gold(i) complexes with tri(tert-butyl)azadiboriridine.

Science.gov (United States)

Shang, Rong; Saito, Souta; Jimenez-Halla, J Oscar C; Yamamoto, Yohsuke

2018-04-17

Direct structural evidence for group 11 metal-mediated B-B bond activation was obtained from reactions of tri(tert-butyl)azadiboriridine (1) with AuCl(L) complexes. The AuCl(SMe2) reaction afforded [η2-B,B-B(tBu)N(tBu)B(tBu)]AuCl (2) by ligand displacement. More donating phosphines as co-ligands led to B-B bond cleavage accompanied by either halide or L migration to form boron-gold complexes 3 (L = PPh3) and 4 (L = PMe3). A similar product 5, which is isostructural to 4, was obtained by the addition of dimethylaminopyridine (DMAP) to 2-4. Complexes 2-5 constitute rare examples of metal complexes bearing two Lewis acidic centres. The effect of the boryl ligand was demonstrated in the formation of a gold(i) complex 6 bearing a 5-membered heterocycle from 3 and tert-butylisonitrile. Plausible reaction mechanisms that led to these complexes and their bonding situation were explored computationally at the DFT level.

Imidazoline and imidazolidine nitroxides as controlling agents in nitroxide-mediated pseudoliving radical polymerization

Science.gov (United States)

Edeleva, M. V.; Marque, S. R. A.; Bagryanskaya, E. G.

2018-04-01

Controlled, or pseudoliving, radical polymerization provides unique opportunities for the synthesis of structurally diverse polymers with a narrow molecular-weight distribution. These reactions occur under relatively mild conditions with broad tolerance to functional groups in the monomers. The nitroxide-mediated pseudoliving radical polymerization is of particular interest for the synthesis of polymers for biomedical applications. This review briefly describes one of the mechanisms of controlled radical polymerization. The studies dealing with the use of imidazoline and imidazolidine nitroxides as controlling agents for nitroxide-mediated pseudoliving radical polymerization of various monomers are summarized and analyzed. The publications addressing the key steps of the controlled radical polymerization in the presence of imidazoline and imidazolidine nitroxides and new approaches to nitroxide-mediated polymerization based on protonation of both nitroxides and monomers are considered. The bibliography includes 154 references.

Polyol-mediated synthesis of copper indium sulphide by solvothermal process

International Nuclear Information System (INIS)

Gorai, S.; Chaudhuri, S.

2005-01-01

A simple polyol-mediated solvothermal method has been proposed to synthesize copper indium sulphide. XRD studies reveal that the products are well crystallized. SEM indicates rod-like (with different aspect ratio) and star-shaped flake-like morphology of the products. The products are also characterized by optical studies and compositional analysis (XRF). XRF results show the formation of stoichiometric and non-stoichiometric copper indium sulphides depending on the reaction conditions

(Injustice contexts and work satisfaction: The mediating role of justice perceptions

Directory of Open Access Journals (Sweden)

Zhou, Q.

2012-01-01

Full Text Available This study explores the impact of the social context, namely (injustice climate and target, in workers' justice perceptions and satisfaction. Individual's justice judgments are expected to mediate the relationship of (injustice climate and target with work satisfaction. We found mediation effects of procedural justice in the relationship between justice climate and satisfaction, and interactional justice in the relationship between injustice target and satisfaction. Distributive justice does not affect the relationship between the (injustice context and satisfaction. Findings demonstrate the relevance of framing organizational justice in a socially contextualized perspective since they seem to influence individual justice reactions and work attitudes. Using an experimental methodology, it was possible to explore the role of seldom studied contextual variables.

Causal mediation analysis with multiple causally non-ordered mediators.

Science.gov (United States)

Taguri, Masataka; Featherstone, John; Cheng, Jing

2018-01-01

In many health studies, researchers are interested in estimating the treatment effects on the outcome around and through an intermediate variable. Such causal mediation analyses aim to understand the mechanisms that explain the treatment effect. Although multiple mediators are often involved in real studies, most of the literature considered mediation analyses with one mediator at a time. In this article, we consider mediation analyses when there are causally non-ordered multiple mediators. Even if the mediators do not affect each other, the sum of two indirect effects through the two mediators considered separately may diverge from the joint natural indirect effect when there are additive interactions between the effects of the two mediators on the outcome. Therefore, we derive an equation for the joint natural indirect effect based on the individual mediation effects and their interactive effect, which helps us understand how the mediation effect works through the two mediators and relative contributions of the mediators and their interaction. We also discuss an extension for three mediators. The proposed method is illustrated using data from a randomized trial on the prevention of dental caries.

Cooperative organocatalysis of Mukaiyama-type aldol reactions by thioureas and nitro compounds

KAUST Repository

Bukhriakov, Konstantin; Desyatkin, Victor G.; Rodionov, Valentin

2016-01-01

A unique organocatalytic system for Mukaiyama-type aldol reactions based on the cooperative action of nitro compounds and thioureas has been identified. This system is compatible with a wide range of substrates and does not require low temperatures, inert atmospheres, or an aqueous workup. A catalytic mechanism based on nitro group-mediated silyl cation transfer has been proposed. © The Royal Society of Chemistry 2016.

Cooperative organocatalysis of Mukaiyama-type aldol reactions by thioureas and nitro compounds

KAUST Repository

Bukhriakov, Konstantin

2016-05-16

A unique organocatalytic system for Mukaiyama-type aldol reactions based on the cooperative action of nitro compounds and thioureas has been identified. This system is compatible with a wide range of substrates and does not require low temperatures, inert atmospheres, or an aqueous workup. A catalytic mechanism based on nitro group-mediated silyl cation transfer has been proposed. © The Royal Society of Chemistry 2016.

Production of Organic Grain Coatings by Surface-Mediated Reactions and the Consequences of This Process for Meteoritic Constituents

Science.gov (United States)

Nuth, Joseph A., III; Johnson, Natasha M.

2011-01-01

When hydrogen, nitrogen and CO are exposed to amorphous iron silicate surfaces at temperatures between 500 - 900K, a carbonaceous coating forms via Fischer-Tropsch type reactions. Under normal circumstances such a catalytic coating would impede or stop further reaction. However, we find that this coating is a better catalyst than the amorphous iron silicates that initiate these reactions. The formation of a self-perpetuating catalytic coating on grain surfaces could explain the rich deposits of macromolecular carbon found in primitive meteorites and would imply that protostellar nebulae should be rich in organic material. Many more experiments are needed to understand this chemical system and its application to protostellar nebulae.

Stable isotope tracer marking of individual boll weevils

International Nuclear Information System (INIS)

James, W.D.; Showler, A.T.; Armstrong, J.S.; Westbrook, J.K.

2006-01-01

Stable isotope markers have been used to study animal nutrition for several decades and more recently to study the foraging and cultural habits of imported fire ants. In this work, we have extended that effort to evaluate the potential for marking boll weevils, Anthonomus grandis grandis Boheman (Coleoptera: Curculionidae), with the rare earth element samarium to aid in studies of insect invasion and pest eradication protocols. Neutron activation analysis (NAA) was performed on the marked boll weevils as well as plant material from the cotton squares on which the insects were fed. Samarium levels in non-dosed insects average about 20 ng/g or about 100 pg total element per insect. Our computed average determination limit was 36 pg samarium/weevil. The determination limit for cotton plant squares and leaves averaged 3.5 ng/g and 8.2 ng/g, respectively. These initial results indicate the NAA method is capable of identifying individual marked insects which have assimilated 1 ng of samarium, a ten-fold increase in content over average blank values. (author)

Rac1 mediates cytokine-stimulated hemocyte spreading via prostaglandin biosynthesis in the beet armyworm, Spodoptera exigua

Science.gov (United States)

Cell spreading is an integral component of insect hemocytic immune reactions to infections and invasions. Cell spreading is accomplished by cytoskeleton rearrangement, which is activated by three major immune mediators, biogenic monoamines, plasmatocyte-spreading peptide (PSP), and eicosanoids, part...

Leprosy type 1 reactions and erythema nodosum leprosum Reações hansênicas do tipo 1 e eritema nodoso hansênico

OpenAIRE

Indira P. Kahawita; Stephen L. Walker; Diana N.J. Lockwood

2008-01-01

Leprosy reactions are a major cause of nerve damage and morbidity in a significant proportion of leprosy patients. Reactions are immunologically mediated and can occur even after successful completion of multi-drug therapy. This review focuses on the epidemiology, pathology and treatment of leprosy type 1 reactions, erythema nodosum leprosum and silent neuropathy.As reações hansênicas são a principal causa de dano e morbidade neural em grande parte dos pacientes hansênicos. São imunomediadas ...

DNAzyme-Based Logic Gate-Mediated DNA Self-Assembly.

Science.gov (United States)

Zhang, Cheng; Yang, Jing; Jiang, Shuoxing; Liu, Yan; Yan, Hao

2016-01-13

Controlling DNA self-assembly processes using rationally designed logic gates is a major goal of DNA-based nanotechnology and programming. Such controls could facilitate the hierarchical engineering of complex nanopatterns responding to various molecular triggers or inputs. Here, we demonstrate the use of a series of DNAzyme-based logic gates to control DNA tile self-assembly onto a prescribed DNA origami frame. Logic systems such as "YES," "OR," "AND," and "logic switch" are implemented based on DNAzyme-mediated tile recognition with the DNA origami frame. DNAzyme is designed to play two roles: (1) as an intermediate messenger to motivate downstream reactions and (2) as a final trigger to report fluorescent signals, enabling information relay between the DNA origami-framed tile assembly and fluorescent signaling. The results of this study demonstrate the plausibility of DNAzyme-mediated hierarchical self-assembly and provide new tools for generating dynamic and responsive self-assembly systems.

Organolanthanide reagents and the Mukaiyama reaction

International Nuclear Information System (INIS)

Gong, L.

1989-01-01

The bis(pentamethylcyclopentadienyl) lutetium halide complex [(C 5 Me 5 ) 2 LuCl/center dot/THF] was synthesized and characterized. The crystal structure of this complex shows that the Lu is at the center of a distorted tetrahedron consisting of the centroids of two cyclopentadienyl rings, the oxygen atom of a tetrahydrofuran molecule and a chlorine atom. 1 H NMR studies of toluene-d 8 solutions of (C 5 Me 5 LuCl(THF) + THF, (TMS 2 CP) 2 LuCl(THF) + THF, and (MeCp) 2 LuCl(THF) + THF at various temperatures showed exchange processes between co- ordinated THF and free THF with average values of ΔG/sup ne/ of 13.0 /+-/ 0.3 kcal/mol, 11.1 /+-/ 0.1 kcal/mol and 2 Cp) 2 YbCl dimer, silyl enol ethers (R 1 R 2 C = C(OR 3 )OSiMe 3 )) react with benzaldehyde smoothly in dichloromethane at room temperature, giving >99% of the aldol silyl ether (isolated yield: 90%) within 3 h. At /minus/78/degrees/C, the reaction gives kinetically controlled diastereoselectivity, which was not observed in the TiCl 4 -mediated aldol reaction. The use of organoytterbium enolates shows promise result with respect to increased stereoselectivity, and indicates the importance of the bulky ligands on the metal center. In addition, Yb(III) species can retard retroaldol reaction owing to its mild Lewis acidity. 118 refs., 14 figs., 30 tabs

Effect of Modifying Factors on Radiosensitive Biochemical Reactions

Energy Technology Data Exchange (ETDEWEB)

Romantsev, E. F.; Filippovich, I. V.; Zhulanova, Z. I.; Blokhina, V. D.; Trebenok, Z. A.; Kolesnikov, E. E.; Sheremetyevskaya, T. N.; Nikolsky, A. V.; Zymaleva, O. G. [Institute of Biophysics, USSR Ministry of Health, Moscow, USSR (Russian Federation)

1971-03-15

Some of the radioprotective aminothiols are now routine pharmacopoeial drugs and are used in clinics to decrease the radiation reaction which appears as a side effect during the radiotherapy of cancer. The action of effective modifying agents on radiosensitive biochemical reactions in the organisms of mammals, in principle, cannot be different from the same effects of the protectors on biochemical systems of the human organism. The effect of modifying agents is mediated by biochemical systems. The administration of radioprotective doses of MEA to rats before irradiation results in a significant normalization of the excretion in urine of degradation products of nucleic acids (so-called Dische-positive compounds), the excretion of which sharply rises after irradiation. The curve of the radioprotective effect of MEA (survival rate after administration of radioprotectors at different intervals of time) completely corresponds to curves of the accumulation of MEA which is bound (by mixed disulphide links) to the proteins of liver mitochondria, to proteins of the nuclear-sap, to the hyaloplasm of rat thymus and to the nuclear ribosomes of the spleen. After MEA administration the curve of the biosynthesis of deoxycytidine represents a mirror reflection of the curve of MEA bound to proteins of the thymus hyaloplasm by means of mixed disulphide links. The mechanism of action of such modifying factors as MEA in experiments on mammals is mediated to a great degree through the temporary formation of mixed disulphide links between the aminothiol and the protein component of enzymes in different biochemical systems. (author)

Mediatization

DEFF Research Database (Denmark)

Hjarvard, Stig

2017-01-01

Mediatization research shares media effects studies' ambition of answering the difficult questions with regard to whether and how media matter and influence contemporary culture and society. The two approaches nevertheless differ fundamentally in that mediatization research seeks answers...... to these general questions by distinguishing between two concepts: mediation and mediatization. The media effects tradition generally considers the effects of the media to be a result of individuals being exposed to media content, i.e. effects are seen as an outcome of mediated communication. Mediatization...... research is concerned with long-term structural changes involving media, culture, and society, i.e. the influences of the media are understood in relation to how media are implicated in social and cultural changes and how these processes come to create new conditions for human communication and interaction...

Gold nanoparticle enhanced fluorescence anisotropy for the assay of single nucleotide polymorphisms (SNPs) based on toehold-mediated strand-displacement reaction.

Science.gov (United States)

Wang, Xinyi; Zou, Mingjian; Huang, Hongduan; Ren, Yuqian; Li, Limei; Yang, Xiaoda; Li, Na

2013-03-15

We developed a highly differentiating, homogeneous gold nanoparticle (AuNP) enhanced fluorescence anisotropic method for single nucleotide polymorphism (SNP) detection at nanomolar level using toehold-mediated strand-displacement reaction. The template strand, containing a toehold domain with an allele-specific site, was immobilized on the surface of AuNPs, and the solution fluorescence anisotropy was markedly enhanced when the fluorescein-labeled blocking DNA was attached to the AuNP via hybridization. Strand-displacement by the target ssDNA strand resulted in detachment of fluorescein-labeled DNA from AuNPs, and thus decreased fluorescence anisotropy. The drastic kinetic difference in strand-displacement from toehold design was used to distinguish between the perfectly matched and the single-base mismatched strands. Free energy changes were calculated to elucidate the dependence of the differentiation ability on the mutation site in the toehold region. A solid negative signal change can be obtained for single-base mismatched strand in the dynamic range of the calibration curve, and a more than 10-fold signal difference can still be observed in a mixed solution containing 100 times the single-base mismatched strand, indicating the good specificity of the method. This proposed method can be performed with a standard spectrofluorimeter in a homogeneous and cost-effective manner, and has the potential to be extended to the application of fluorescence anisotropy method of SNP detection. Copyright © 2012 Elsevier B.V. All rights reserved.

Public reaction to Chikungunya outbreaks in Italy-Insights from an extensive novel data streams-based structural equation modeling analysis.

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Naim Mahroum

Full Text Available The recent outbreak of Chikungunya virus in Italy represents a serious public health concern, which is attracting media coverage and generating public interest in terms of Internet searches and social media interactions. Here, we sought to assess the Chikungunya-related digital behavior and the interplay between epidemiological figures and novel data streams traffic. Reaction to the recent outbreak was analyzed in terms of Google Trends, Google News and Twitter traffic, Wikipedia visits and edits, and PubMed articles, exploiting structural modelling equations. A total of 233,678 page-views and 150 edits on the Italian Wikipedia page, 3,702 tweets, 149 scholarly articles, and 3,073 news articles were retrieved. The relationship between overall Chikungunya cases, as well as autochthonous cases, and tweets production was found to be fully mediated by Chikungunya-related web searches. However, in the allochthonous/imported cases model, tweet production was not found to be significantly mediated by epidemiological figures, with web searches still significantly mediating tweet production. Inconsistent relationships were detected in mediation models involving Wikipedia usage as a mediator variable. Similarly, the effect between news consumption and tweets production was suppressed by the Wikipedia usage. A further inconsistent mediation was found in the case of the effect between Wikipedia usage and tweets production, with web searches as a mediator variable. When adjusting for the Internet penetration index, similar findings could be obtained, with the important exception that in the adjusted model the relationship between GN and Twitter was found to be partially mediated by Wikipedia usage. Furthermore, the link between Wikipedia usage and PubMed/MEDLINE was fully mediated by GN, differently from what was found in the unadjusted model. In conclusion-a significant public reaction to the current Chikungunya outbreak was documented. Health authorities

Public reaction to Chikungunya outbreaks in Italy-Insights from an extensive novel data streams-based structural equation modeling analysis.

Science.gov (United States)

Mahroum, Naim; Adawi, Mohammad; Sharif, Kassem; Waknin, Roy; Mahagna, Hussein; Bisharat, Bishara; Mahamid, Mahmud; Abu-Much, Arsalan; Amital, Howard; Luigi Bragazzi, Nicola; Watad, Abdulla

2018-01-01

The recent outbreak of Chikungunya virus in Italy represents a serious public health concern, which is attracting media coverage and generating public interest in terms of Internet searches and social media interactions. Here, we sought to assess the Chikungunya-related digital behavior and the interplay between epidemiological figures and novel data streams traffic. Reaction to the recent outbreak was analyzed in terms of Google Trends, Google News and Twitter traffic, Wikipedia visits and edits, and PubMed articles, exploiting structural modelling equations. A total of 233,678 page-views and 150 edits on the Italian Wikipedia page, 3,702 tweets, 149 scholarly articles, and 3,073 news articles were retrieved. The relationship between overall Chikungunya cases, as well as autochthonous cases, and tweets production was found to be fully mediated by Chikungunya-related web searches. However, in the allochthonous/imported cases model, tweet production was not found to be significantly mediated by epidemiological figures, with web searches still significantly mediating tweet production. Inconsistent relationships were detected in mediation models involving Wikipedia usage as a mediator variable. Similarly, the effect between news consumption and tweets production was suppressed by the Wikipedia usage. A further inconsistent mediation was found in the case of the effect between Wikipedia usage and tweets production, with web searches as a mediator variable. When adjusting for the Internet penetration index, similar findings could be obtained, with the important exception that in the adjusted model the relationship between GN and Twitter was found to be partially mediated by Wikipedia usage. Furthermore, the link between Wikipedia usage and PubMed/MEDLINE was fully mediated by GN, differently from what was found in the unadjusted model. In conclusion-a significant public reaction to the current Chikungunya outbreak was documented. Health authorities should be aware of

Clinical Practice Guidelines for Diagnosis and Management of Hypersensitivity Reactions to Contrast Media.

Science.gov (United States)

Rosado Ingelmo, A; Doña Diaz, I; Cabañas Moreno, R; Moya Quesada, M C; García-Avilés, C; García Nuñez, I; Martínez Tadeo, J I; Mielgo Ballesteros, R; Ortega-Rodríguez, N; Padial Vilchez, M A; Sánchez-Morillas, L; Vila Albelda, C; Moreno Rodilla, E; Torres Jaén, M J

2016-01-01

The objective of these guidelines is to ensure efficient and effective clinical practice. The panel of experts who produced this consensus document developed a research protocol based on a review of the literature. The prevalence of allergic reactions to iodinated contrast media (ICM) is estimated to be 1:170 000, that is, 0.05%-0.1% of patients undergoing radiologic studies with ICM (more than 75 million examinations per year worldwide). Hypersensitivity reactions can appear within the first hour after administration (immediate reactions) or from more than 1 hour to several days after administration (nonimmediate or delayed reactions). The risk factors for immediate reactions include poorly controlled bronchial asthma, concomitant medication (eg, angiotensin-converting enzyme inhibitors, ß-blockers, and proton-pump inhibitors), rapid administration of the ICM, mastocytosis, autoimmune diseases, and viral infections. The most common symptoms of immediate reactions are erythema and urticaria with or without angioedema, which appear in more than 70% of patients. Maculopapular rash is the most common skin feature of nonimmediate reactions (30%-90%). Skin and in vitro tests should be performed for diagnosis of both immediate and nonimmediate reactions. The ICM to be administered will therefore be chosen depending on the results of these tests, the ICM that induced the reaction (when known), the severity of the reaction, the availability of alternative ICM, and the information available on potential ICM cross-reactivity. Another type of contrast media, gadolinium derivatives, is used used for magnetic resonance imaging. Although rare, IgE-mediated reactions to gadolinium derivatives have been reported.

Highly selective detection of single-nucleotide polymorphisms using a quartz crystal microbalance biosensor based on the toehold-mediated strand displacement reaction.

Science.gov (United States)

Wang, Dingzhong; Tang, Wei; Wu, Xiaojie; Wang, Xinyi; Chen, Gengjia; Chen, Qiang; Li, Na; Liu, Feng

2012-08-21

Toehold-mediated strand displacement reaction (SDR) is first introduced to develop a simple quartz crystal microbalance (QCM) biosensor without an enzyme or label at normal temperature for highly selective and sensitive detection of single-nucleotide polymorphism (SNP) in the p53 tumor suppressor gene. A hairpin capture probe with an external toehold is designed and immobilized on the gold electrode surface of QCM. A successive SDR is initiated by the target sequence hybridization with the toehold domain and ends with the unfolding of the capture probe. Finally, the open-loop capture probe hybridizes with the streptavidin-coupled reporter probe as an efficient mass amplifier to enhance the QCM signal. The proposed biosensor displays remarkable specificity to target the p53 gene fragment against single-base mutant sequences (e.g., the largest discrimination factor is 63 to C-C mismatch) and high sensitivity with the detection limit of 0.3 nM at 20 °C. As the crucial component of the fabricated biosensor for providing the high discrimination capability, the design rationale of the capture probe is further verified by fluorescence sensing and atomic force microscopy imaging. Additionally, a recovery of 84.1% is obtained when detecting the target sequence in spiked HeLa cells lysate, demonstrating the feasibility of employing this biosensor in detecting SNPs in biological samples.

[Mediating effect of mental elasticity on occupational stress and depression in female nurses].

Science.gov (United States)

Wang, Y W; Liu, G Z; Zhou, X T; Sheng, P J; Cui, F F; Shi, T

2017-06-20

Objective: To investigate the interaction between mental elasticityand occupational stress and depressionin female nurses and the mediating effect of mental elasticity, as well as the functioning way of mental elasticity in occupational stress-depression. Methods: From August to October, 2015, cluster sampling was used to select 122 female nurses in a county-level medical institution as study subjects. The Connor-Davidson Resilience Scale (CD-RISC) , Occupational Stress Inventory-Revised Edition (OSI-R) , and Self-Rating Depression Scale (SDS) were used to collect the data on mental elasticity, occupational stress, and depression and analyze their correlation and mediating effect. Results: The 122 female nurses had a mean mental elasticity score of 62.4±15.1, which was significantly lower than the Chinese norm (65.4±13.9) ( P occupational stress and depression ( r =-0.559 and -0.559, both P Occupational stress and the two subscales mental stress reaction and physical stress reaction were positively correlated with depression ( r =0.774, 0.734, and 0.725, all P occupational stress had a positive predictive effect on depression ( β =0.744, P occupational stress on depression and a significant mediating effect of mental elasticity ( a =-0.527, b =-0.227, c =0.744, c '=0.627; all P occupational stress and depression and can alleviate the adverse effect of occupational stress and reduce the development of depression.

Halogen-Mediated Conversion of Hydrocarbons to Commodities.

Science.gov (United States)

Lin, Ronghe; Amrute, Amol P; Pérez-Ramírez, Javier

2017-03-08

Halogen chemistry plays a central role in the industrial manufacture of various important chemicals, pharmaceuticals, and polymers. It involves the reaction of halogens or halides with hydrocarbons, leading to intermediate compounds which are readily converted to valuable commodities. These transformations, predominantly mediated by heterogeneous catalysts, have long been successfully applied in the production of polymers. Recent discoveries of abundant conventional and unconventional natural gas reserves have revitalized strong interest in these processes as the most cost-effective gas-to-liquid technologies. This review provides an in-depth analysis of the fundamental understanding and applied relevance of halogen chemistry in polymer industries (polyvinyl chloride, polyurethanes, and polycarbonates) and in the activation of light hydrocarbons. The reactions of particular interest include halogenation and oxyhalogenation of alkanes and alkenes, dehydrogenation of alkanes, conversion of alkyl halides, and oxidation of hydrogen halides, with emphasis on the catalyst, reactor, and process design. Perspectives on the challenges and directions for future development in this exciting field are provided.

Interpreter-mediated dentistry.

Science.gov (United States)

Bridges, Susan; Drew, Paul; Zayts, Olga; McGrath, Colman; Yiu, Cynthia K Y; Wong, H M; Au, T K F

2015-05-01

The global movements of healthcare professionals and patient populations have increased the complexities of medical interactions at the point of service. This study examines interpreter mediated talk in cross-cultural general dentistry in Hong Kong where assisting para-professionals, in this case bilingual or multilingual Dental Surgery Assistants (DSAs), perform the dual capabilities of clinical assistant and interpreter. An initial language use survey was conducted with Polyclinic DSAs (n = 41) using a logbook approach to provide self-report data on language use in clinics. Frequencies of mean scores using a 10-point visual analogue scale (VAS) indicated that the majority of DSAs spoke mainly Cantonese in clinics and interpreted for postgraduates and professors. Conversation Analysis (CA) examined recipient design across a corpus (n = 23) of video-recorded review consultations between non-Cantonese speaking expatriate dentists and their Cantonese L1 patients. Three patterns of mediated interpreting indicated were: dentist designated expansions; dentist initiated interpretations; and assistant initiated interpretations to both the dentist and patient. The third, rather than being perceived as negative, was found to be framed either in response to patient difficulties or within the specific task routines of general dentistry. The findings illustrate trends in dentistry towards personalized care and patient empowerment as a reaction to product delivery approaches to patient management. Implications are indicated for both treatment adherence and the education of dental professionals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Direct asymmetric vinylogous aldol reaction of allyl ketones with isatins: Divergent synthesis of 3-hydroxy-2-oxindole derivatives

KAUST Repository

Zhu, Bo; Zhang, Wen; Lee, Richmond; Han, Zhiqiang; Yang, Wenguo; Tan, Davin; Huang, Kuo-Wei; Jiang, Zhiyong

2013-01-01

6 in 1: The highly enantioselective title reaction is mediated by a bifunctional catalyst and leads to E-configured vinylogous aldol products (see scheme). These products are used as common intermediates in the synthesis of six biologically active 3

Photoluminescence and spectroscopic dependence of fluorophosphate glasses on samarium ions concentration and the induced defects by gamma irradiation

Energy Technology Data Exchange (ETDEWEB)

Marzouk, M.A., E-mail: marzouk_nrc@yahoo.com [Glass Research Department, National Research Centre, 33 El Bohouth Street (former EL Tahrir), P.O. 12622, Dokki, Giza (Egypt); Hamdy, Y.M. [Spectroscopy Department, National Research Centre, 33 El Bohouth Street (former EL Tahrir), P.O. 12622, Dokki, Giza (Egypt); ElBatal, H.A. [Glass Research Department, National Research Centre, 33 El Bohouth Street (former EL Tahrir), P.O. 12622, Dokki, Giza (Egypt); Ezz ElDin, F.M. [National Institute for Radiation Research & Technology, Nasr City, Cairo (Egypt)

2015-10-15

Combined optical, FTIR and photoluminescence spectra of varying Sm{sup 3+} ions in NaF–AlF{sub 3}–phosphate glasses were investigated before and after successive gamma irradiation. Optical (UV–visible) absorption of the base undoped glass reveals UV absorption which becomes broadened and strong with progressive gamma irradiation. The UV absorption of the undoped glass is related to unavoidable trace iron impurity (Fe{sup 3+}) contaminated within the chemicals used for its preparation. Upon gamma irradiation, ferrous ions present in noticeable percent within the impurity due to the reducing nature of phosphate glass interact with positive holes during the irradiation process and are transformed to ferric ions through photochemical reactions and the additionally formed Fe{sup 3+} ions impart their characteristic strong absorption in the UV region. Sm{sup 3+} containing glasses show characteristic small peaks arranged into two regions from about 350 to 900 nm and from about 1000 to 1600 nm. Such absorption peaks are more distinct with the increase of Sm{sub 2}O{sub 3} content. Most of the limited number of absorption peaks are due to transitions from the {sup 6}H{sub 5/2} level to the various excited {sup 2s+1}L{sub J} levels. The majority of the transitions in the spectra are assumed to originate from induced electric dipole (ED) interactions with the selection rule ∆J≤6. The intense band {sup 6}P{sub 3/2}←{sup 6}H{sub 5/2} around 25,000 cm{sup −1} (~400 nm) is spin-allowed. The emission spectra of Sm{sup 2+} ions were recorded under the excitation wavelength of 402 nm for all prepared Sm{sub 2}O{sub 3}-containing glasses. The photoluminescence spectra show four emission lines, of which three consist of strong bands while the last line is a weak band. The wavelengths of the four luminescence peaks occur at about 560, 596, 642 and 702 nm and they are assigned to transitions from {sup 4}G{sub 5/2} to {sup 6}H{sub 5/2}, {sup 6}H{sub 7/2}, {sup 6}H{sub 9

Vaginal toxic shock reaction triggering desquamative inflammatory vaginitis.

Science.gov (United States)

Pereira, Nigel; Edlind, Thomas D; Schlievert, Patrick M; Nyirjesy, Paul

2013-01-01

The study aimed to report 2 cases of desquamative inflammatory vaginitis associated with toxic shock syndrome toxin 1 (TSST-1)-producing Staphylococcus aureus strains. Case report of 2 patients, 1 with an acute and 1 with a chronic presentation, diagnosed with desquamative inflammatory vaginitis on the basis of clinical findings and wet mount microscopy. Pretreatment and posttreatment vaginal bacterial and yeast cultures were obtained. Pretreatment vaginal bacterial cultures from both patients grew TSST-1-producing S. aureus. Subsequent vaginal bacterial culture results after oral antibiotic therapy were negative. Desquamative inflammatory vaginitis may be triggered through TSST-1-mediated vaginal toxic shock reaction.