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Sample records for hydrolytic kinetic resolution

  1. Kinetic investigation on enantioselective hydrolytic resolution of ...

    African Journals Online (AJOL)

    Kinetic investigation on enantioselective hydrolytic resolution of epichlorohydrin by crude epoxide hydrolase from domestic duck liver. X Ling, D Lu, J Wang, J Chen, L Ding, J Chen, H Chai, P Ouyang ...

  2. Mechanistic basis for high stereoselectivity and broad substrate scope in the (salen)Co(III)-catalyzed hydrolytic kinetic resolution.

    Science.gov (United States)

    Ford, David D; Nielsen, Lars P C; Zuend, Stephan J; Musgrave, Charles B; Jacobsen, Eric N

    2013-10-16

    In the (salen)Co(III)-catalyzed hydrolytic kinetic resolution (HKR) of terminal epoxides, the rate- and stereoselectivity-determining epoxide ring-opening step occurs by a cooperative bimetallic mechanism with one Co(III) complex acting as a Lewis acid and another serving to deliver the hydroxide nucleophile. In this paper, we analyze the basis for the extraordinarily high stereoselectivity and broad substrate scope observed in the HKR. We demonstrate that the stereochemistry of each of the two (salen)Co(III) complexes in the rate-determining transition structure is important for productive catalysis: a measurable rate of hydrolysis occurs only if the absolute stereochemistry of each of these (salen)Co(III) complexes is the same. Experimental and computational studies provide strong evidence that stereochemical communication in the HKR is mediated by the stepped conformation of the salen ligand, and not the shape of the chiral diamine backbone of the ligand. A detailed computational analysis reveals that the epoxide binds the Lewis acidic Co(III) complex in a well-defined geometry imposed by stereoelectronic rather than steric effects. This insight serves as the basis of a complete stereochemical and transition structure model that sheds light on the reasons for the broad substrate generality of the HKR.

  3. Hydrolytic kinetic resolution of the enantiomers of the structural isomers trans-1-phenylpropene oxide and (2,3-epoxypropyl) benzene by yeast epoxide hydrolase

    CSIR Research Space (South Africa)

    Lotter, J

    2004-08-01

    Full Text Available Kinetic resolution of the enantiomers of trans-1-phenylpropene oxide and (2,3-epoxypropyl)benzene was achieved by yeasts from the genus Rhodotorula. The resolution of trans-1-phenylpropene oxide by Rhodotorula glutinis UOFS Y-0123 yielded (1R, 2R...

  4. (R,S)-2-chlorophenoxyl pyrazolides as novel substrates for improving lipase-catalyzed hydrolytic resolution.

    Science.gov (United States)

    Kao, Min-fang; Lu, Pei-yu; Kao, Jou-yan; Wang, Pei-yun; Wu, An-chi; Tsai, Shau-Wei

    2012-01-01

    The best reaction condition of Candida antartica lipase B as biocatalyst, 3-(2-pyridyl)pyrazole as leaving azole, and water-saturated methyl t-butyl ether as reaction medium at 45°C were first selected for performing the hydrolytic resolution of (R,S)-2-(4-chlorophenoxyl) azolides (1-4). In comparison with the kinetic resolution of (R,S)-2-phenylpropionyl 3-(2-pyridyl)pyrazolide or (R,S)-α-methoxyphenylacetyl 3-(2-pyridyl)pyrazolide at the same reaction condition, excellent enantioselectivity with more than two order-of-magnitudes higher activity for each enantiomer was obtained. The resolution was then extended to other (R,S)-3-(2-pyridyl)pyrazolides (5-7) containing 2-chloro, 3-chloro, or 2,4-dichloro substituent, giving good (E > 48) to excellent (E > 100) enantioselectivity. The thermodynamic analysis for 1, 2, and 4-7 demonstrates profound effects of the acyl or leaving moiety on varying enthalpic and entropic contributions to the difference of Gibbs free energies. A thorough kinetic analysis further indicates that on the basis of 6, the excellent enantiomeric ratio for 4 and 7 is due to the higher reactivity of (S)-4 and lower reactivity of (R)-7, respectively. Copyright © 2011 Wiley-Liss, Inc.

  5. Dynamic Ureas with Fast and pH-Independent Hydrolytic Kinetics.

    Science.gov (United States)

    Cai, Kaimin; Ying, Hanze; Cheng, Jianjun

    2018-04-06

    Low cost, high performance hydrolysable polymers are of great importance in biomedical applications and materials industries. While many applications require materials to have a degradation profile insensitive to external pH to achieve consistent release profiles under varying conditions, hydrolysable chemistry techniques developed so far have pH-dependent hydrolytic kinetics. This work reports the design and synthesis of a new type of hydrolysable polymer that has identical hydrolysis kinetics from pH 3 to 11. The unprecedented pH independent hydrolytic kinetics of the aryl ureas were shown to be related to the dynamic bond dissociation controlled hydrolysis mechanism; the resulting hindered poly(aryl urea) can be degraded with a hydrolysis half-life of 10 min in solution. More importantly, these fast degradable hindered aromatic polyureas can be easily prepared by addition polymerization from commercially available monomers and are resistant to hydrolysis in solid form for months under ambient storage conditions. The combined features of good stability in solid state and fast hydrolysis at various pH values is unprecedented in polyurea material, and will have implications for materials design and applications, such as sacrificial coatings and biomaterials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Hydrolytic Activation Kinetics of the Herbicide Benzobicyclon in Simulated Aquatic Systems.

    Science.gov (United States)

    Williams, Katryn L; Tjeerdema, Ronald S

    2016-06-22

    Herbicide resistance is a growing concern for weeds in California rice fields. Benzobicyclon (BZB; 3-(2-chloro-4-(methylsulfonyl)benzoyl)-2-phenylthiobicyclo[3.2.1]oct-2-en-4-one) has proven successful against resistant rice field weeds in Asia. A pro-herbicide, BZB forms the active agent, benzobicyclon hydrolysate (BH), in water; however, the transformation kinetics are not understood for aquatic systems, particularly flooded California rice fields. A quantitative experiment was performed to assess the primary mechanism and kinetics of BZB hydrolysis to BH. Complete conversion to BH was observed for all treatments. Basic conditions (pH 9) enhanced the reaction, with half-lives ranging from 5 to 28 h. Dissolved organic carbon (DOC) hindered transformation, which is consistent with other base-catalyzed hydrolysis reactions. BH was relatively hydrolytically stable, with 18% maximum loss after 5 days. Results indicate BZB is an efficient pro-herbicide under aqueous conditions such as those of a California rice field, although application may be best suited for fields with recirculating tailwater systems.

  7. Kinetic measurements of the hydrolytic degradation of cefixime: effect of Captisol complexation and water-soluble polymers.

    Science.gov (United States)

    Mallick, Subrata; Mondal, Arijit; Sannigrahi, Santanu

    2008-07-01

    We have taken kinetic measurements of the hydrolytic degradation of cefixime, and have studied the effect of Captisol complexation and water-soluble polymers on that degradation. The phase solubility of cefixime in Captisol was determined. Kinetic measurements were carried out as a function of pH and temperature. High-performance liquid chromatography (HPLC) was performed to assay all the samples of phase-solubility analysis and kinetic measurements. Chromatographic separation of the degradation products was also performed by HPLC. FT-IR spectroscopy was used to investigate the presence of any interaction between cefixime and Captisol and soluble polymer. The phase-solubility study showed A(L)-type behaviour. The pH-rate profile of cefixime exhibited a U-shaped profile whilst the degradation of cefixime alone was markedly accelerated with elevated temperature. A strong stabilizing influence of the cefixime-Captisol complexation and hypromellose was observed against aqueous mediated degradation, as compared with povidone and macrogol. The unfavourable effect of povidone and macrogol may have been due to the steric hindrance, which prevented the guest molecule from entering the cyclodextrin cavity, whereas hypromellose did not produce any steric hindrance.

  8. Catalytic Kinetic Resolution of Biaryl Compounds.

    Science.gov (United States)

    Ma, Gaoyuan; Sibi, Mukund P

    2015-08-10

    Biaryl compounds with axial chirality are very common in synthetic chemistry, especially in catalysis. Axially chiral biaryls are important due to their biological activities and extensive applications in asymmetric catalysis. Thus the development of efficient enantioselective methods for their synthesis has attracted considerable attention. This Minireview discusses the progress made in catalytic kinetic resolution of biaryl compounds and chronicles significant advances made recently in catalytic kinetic resolution of biaryl scaffolds. © 2015 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Operational High Resolution Chemical Kinetics Simulation, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Numerical simulations of chemical kinetics are critical to addressing urgent issues in both the developed and developing world. Ongoing demand for higher resolution...

  10. Dynamic kinetic resolution of biaryl atropisomers by chiral dialkylaminopyridine catalysts.

    Science.gov (United States)

    Ma, Gaoyuan; Deng, Chao; Deng, Jun; Sibi, Mukund P

    2018-05-02

    The acylative dynamic kinetic resolution (DKR) of configurationally unstable biaryl atropisomers is achieved by using newly developed chiral dialkylaminopyridine catalysts with fluxional chirality. Various types of biaryl substrates containing phenolic structures were subjected to the DKR to obtain a range of acylated biaryl products with enantiomeric ratios up to 90 : 10.

  11. Fast Search and Adaptive Resolution for Complex Particle Kinetics

    Science.gov (United States)

    Larson, David J.

    2005-10-01

    A new plasma simulation algorithm, intended to bridge the gap between Eulerian fluid and kinetic regimes, is now being used for a variety of applications in ICF and weapon effects. The CPK method (Complex Particle Kinetic) concept [1] uses an ensemble of macro-particles with a Gaussian spatial profile and a Mawellian velocity distribution to represent particle distributions in phase space. Time evolution is modeled by a combination of Lagrangian motion and internal evolution within each individual macro-particle. Collisional particle-particle interactions [2] are facilitated by sorting particles into bins depending of the particle size. Different bin levels are connected by a linked list. Searching for neighboring particles is highly efficient because the search is limited to particles in neighboring bins with the possibility of interaction. The bin structure also allows the computation of various spatial moments at different resolutions. Combining the results of the moment calculations yields information on where and when increased resolution is necessary. We will present details of the particle binning process along with progress towards our goal of simulating the transition from continuum to fully kinetic physics. [1] D. W. Hewett, J. Comp. Phys. 189 (2003). [2] D. J. Larson, J. Comp. Phys. 188 (2003).

  12. Kinetic energy spectra, vertical resolution and dissipation in high-resolution atmospheric simulations.

    Science.gov (United States)

    Skamarock, W. C.

    2017-12-01

    We have performed week-long full-physics simulations with the MPAS global model at 15 km cell spacing using vertical mesh spacings of 800, 400, 200 and 100 meters in the mid-troposphere through the mid-stratosphere. We find that the horizontal kinetic energy spectra in the upper troposphere and stratosphere does not converge with increasing vertical resolution until we reach 200 meter level spacing. Examination of the solutions indicates that significant inertia-gravity waves are not vertically resolved at the lower vertical resolutions. Diagnostics from the simulations indicate that the primary kinetic energy dissipation results from the vertical mixing within the PBL parameterization and from the gravity-wave drag parameterization, with smaller but significant contributions from damping in the vertical transport scheme and from the horizontal filters in the dynamical core. Most of the kinetic energy dissipation in the free atmosphere occurs within breaking mid-latitude baroclinic waves. We will briefly review these results and their implications for atmospheric model configuration and for atmospheric dynamics, specifically that related to the dynamics associated with the mesoscale kinetic energy spectrum.

  13. Influence of the interaction volume on the kinetic energy resolution of a velocity map imaging spectrometer

    International Nuclear Information System (INIS)

    Zhang Peng; Feng Zheng-Peng; Luo Si-Qiang; Wang Zhe

    2016-01-01

    We investigate the influence of the interaction volume on the energy resolution of a velocity map imaging spectrometer. The simulation results show that the axial interaction size has a significant influence on the resolution. This influence is increased for a higher kinetic energy. We further show that the radial interaction size has a minor influence on the energy resolution for the electron or ion with medium energy, but it is crucial for the resolution of the electron or ion with low kinetic energy. By tracing the flight trajectories we show how the electron or ion energy resolution is influenced by the interaction size. (paper)

  14. Hydrolytically stable titanium-45

    DEFF Research Database (Denmark)

    Severin, Gregory; Fonslet, Jesper; Zhuravlev, Fedor

    2014-01-01

    metal-based chemotherapeutics such as cisplatin. The aim of our work has been to produce the radioactive analogue of one of these Ti(IV)-salan compounds, Ti-salan-dipic [2], which has hydro-lytic stability on the order of weeks. Not only will this allow us to shed some light on the still un...... the physical characteristics are extremely desirable: 45Ti has a 3 hour half-life, a positron branching ratio of 85 %, a low Eβmax of 1.04 MeV, and negligible secondary gamma emission. In terms of isotope production, 45Ti is transmuted from naturally mono-isotopic 45Sc by low energy proton irradiation...... to a water-cooled silver plate. The activated foil was dissolved in 4M HCl, dried under argon at 120 oC, and taken back up in 12M HCl. Here, four (i-iv below) different approaches to removing the Ti from the Sc and labeling were taken with varying success. Briefly: i. 45Ti was separated on hydroxamate resin...

  15. Photon-Counting Microwave Kinetic Inductance Detectors (MKIDs) for High Resolution Far-Infrared Spectroscopy

    Data.gov (United States)

    National Aeronautics and Space Administration — We are developing ultrasensitive Microwave Kinetic Inductance Detectors (MKIDs) for high resolution far-infrared spectroscopy applications, with a long-term goal of...

  16. CATALYTIC KINETIC RESOLUTION OF 5-ALKOXY-2(5H)-FURANONES

    OpenAIRE

    FABER, WS; Kok, Johan C; DELANGE, B; FERINGA, BL; Faber, Wijnand S.; Lange, Ben de; Feringa, Bernard

    1994-01-01

    The kinetic resolution of racemic 5-alkoxy-2(5H)-furanones, using a chiral aminoalcohol catalyzed 1-4-addition of arylthiols, was examined. Using various butenolides it was shown that a gamma-alkoxy substituent appears to be essential to reach high enantioselectivities whereas electron-donating substituents in the arylthiols also increase the selectivity. Cinchona alkaloids are the preferred catalysts for the kinetic resolution, with quinine and quinidine leading to the most efficient and sel...

  17. Molecular Imaging of Hydrolytic Enzymes Using PET and SPECT.

    Science.gov (United States)

    Rempel, Brian P; Price, Eric W; Phenix, Christopher P

    2017-01-01

    Hydrolytic enzymes are a large class of biological catalysts that play a vital role in a plethora of critical biochemical processes required to maintain human health. However, the expression and/or activity of these important enzymes can change in many different diseases and therefore represent exciting targets for the development of positron emission tomography (PET) and single-photon emission computed tomography (SPECT) radiotracers. This review focuses on recently reported radiolabeled substrates, reversible inhibitors, and irreversible inhibitors investigated as PET and SPECT tracers for imaging hydrolytic enzymes. By learning from the most successful examples of tracer development for hydrolytic enzymes, it appears that an early focus on careful enzyme kinetics and cell-based studies are key factors for identifying potentially useful new molecular imaging agents.

  18. Kinetic Energy from Supernova Feedback in High-resolution Galaxy Simulations

    Science.gov (United States)

    Simpson, Christine M.; Bryan, Greg L.; Hummels, Cameron; Ostriker, Jeremiah P.

    2015-08-01

    We describe a new method for adding a prescribed amount of kinetic energy to simulated gas modeled on a cartesian grid by directly altering grid cells’ mass and velocity in a distributed fashion. The method is explored in the context of supernova (SN) feedback in high-resolution (˜10 pc) hydrodynamic simulations of galaxy formation. Resolution dependence is a primary consideration in our application of the method, and simulations of isolated explosions (performed at different resolutions) motivate a resolution-dependent scaling for the injected fraction of kinetic energy that we apply in cosmological simulations of a 109 M⊙ dwarf halo. We find that in high-density media (≳50 cm-3) with coarse resolution (≳4 pc per cell), results are sensitive to the initial kinetic energy fraction due to early and rapid cooling. In our galaxy simulations, the deposition of small amounts of SN energy in kinetic form (as little as 1%) has a dramatic impact on the evolution of the system, resulting in an order-of-magnitude suppression of stellar mass. The overall behavior of the galaxy in the two highest resolution simulations we perform appears to converge. We discuss the resulting distribution of stellar metallicities, an observable sensitive to galactic wind properties, and find that while the new method demonstrates increased agreement with observed systems, significant discrepancies remain, likely due to simplistic assumptions that neglect contributions from SNe Ia and stellar winds.

  19. Dual enzymatic dynamic kinetic resolution by Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase and Candida antarctica lipase B

    KAUST Repository

    Karume, Ibrahim

    2016-10-04

    The immobilization of Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase (TeSADH) using sol–gel method enables its use to racemize enantiopure alcohols in organic media. Here, we report the racemization of enantiopure phenyl-ring-containing secondary alcohols using xerogel-immobilized W110A TeSADH in hexane rather than the aqueous medium required by the enzyme. We further showed that this racemization approach in organic solvent was compatible with Candida antarctica lipase B (CALB)-catalyzed kinetic resolution. This compatibility, therefore, allowed a dual enzymatic dynamic kinetic resolution of racemic alcohols using CALB-catalyzed kinetic resolution and W110A TeSADH-catalyzed racemization of phenyl-ring-containing alcohols.

  20. Oxidative kinetic resolution of racemic alcohols catalyzed by chiral ferrocenyloxazolinylphosphine-ruthenium complexes.

    Science.gov (United States)

    Nishibayashi, Yoshiaki; Yamauchi, Akiyoshi; Onodera, Gen; Uemura, Sakae

    2003-07-25

    Oxidative kinetic resolution of racemic secondary alcohols by using acetone as a hydrogen acceptor in the presence of a catalytic amount of [RuCl(2)(PPh(3))(ferrocenyloxazolinylphosphine)] (2) proceeds effectively to recover the corresponding alcohols in high yields with an excellent enantioselectivity. When 1-indanol is employed as a racemic alcohol, the oxidation proceeds quite smoothly even in the presence of 0.0025 mol % of the catalyst 2 to give an optically active 1-indanol in good yield with high enantioselectivity (up to 94% ee), where turnover frequency (TOF) exceeds 80,000 h(-1). From a practical viewpoint, the kinetic resolution is investigated in a large scale, optically pure (S)-1-indanol (75 g, 56% yield, >99% ee) being obtained from racemic 1-indanol (134 g) by employing this kinetic resolution method twice.

  1. Recent Advances in Dynamic Kinetic Resolution by Chiral Bifunctional (Thiourea- and Squaramide-Based Organocatalysts

    Directory of Open Access Journals (Sweden)

    Pan Li

    2016-10-01

    Full Text Available The organocatalysis-based dynamic kinetic resolution (DKR process has proved to be a powerful strategy for the construction of chiral compounds. In this feature review, we summarized recent progress on the DKR process, which was promoted by chiral bifunctional (thiourea and squaramide catalysis via hydrogen-bonding interactions between substrates and catalysts. A wide range of asymmetric reactions involving DKR, such as asymmetric alcoholysis of azlactones, asymmetric Michael–Michael cascade reaction, and enantioselective selenocyclization, are reviewed and demonstrate the efficiency of this strategy. The (thiourea and squaramide catalysts with dual activation would be efficient for more unmet challenges in dynamic kinetic resolution.

  2. Synthesis of Chiral Cyclic Carbonates via Kinetic Resolution of Racemic Epoxides and Carbon Dioxide

    Directory of Open Access Journals (Sweden)

    Xiao Wu

    2016-01-01

    Full Text Available The catalytic synthesis of cyclic carbonates using carbon dioxide as a C1-building block is a highly active area of research. Here, we review the catalytic production of enantiomerically enriched cyclic carbonates via kinetic resolution of racemic epoxides catalysed by metal-containing catalyst systems.

  3. Diels-Alder cycloaddition strategy for kinetic resolution of chiral pyrazolidinones.

    Science.gov (United States)

    Sibi, Mukund P; Kawashima, Keisuke; Stanley, Levi M

    2009-09-03

    A rare example of the application of a catalytic, enantioselective Diels-Alder cycloaddition to affect a kinetic resolution has been developed. Chiral pyrazolidinones are resolved with high selectivity through a process that utilizes a relay of stereochemical information from a permanent chiral center to a fluxional chiral center to enhance the inherent selectivity of the chiral Lewis acid catalyst.

  4. CATALYTIC KINETIC RESOLUTION OF 5-ALKOXY-2(5H)-FURANONES

    NARCIS (Netherlands)

    FABER, WS; Kok, Johan C; DELANGE, B; FERINGA, BL; Faber, Wijnand S.; Lange, Ben de; Feringa, Bernard

    1994-01-01

    The kinetic resolution of racemic 5-alkoxy-2(5H)-furanones, using a chiral aminoalcohol catalyzed 1-4-addition of arylthiols, was examined. Using various butenolides it was shown that a gamma-alkoxy substituent appears to be essential to reach high enantioselectivities whereas electron-donating

  5. Kinetic Resolution and Stereoselective Synthesis of 3-Substituted Aspartic Acids by Using Engineered Methylaspartate Ammonia Lyases

    NARCIS (Netherlands)

    Raj, Hans; Szymanski, Wiktor; Villiers, Jandré de; Puthan Veetil, Vinod; Quax, Wim J.; Shimamoto, Keiko; Janssen, Dick B.; Feringa, Ben L.; Poelarends, Gerrit J.

    2013-01-01

    Kinetic resolution and asymmetric synthesis of various valuable 3-substituted aspartic acids, which were obtained in fair to good yields with diastereomeric ratio values of up to >98:2 and enantiomeric excess values of up to >99 %, by using engineered methylaspartate ammonia lyases are described.

  6. High resolution kinetic beam schemes in generalized coordinates for ideal quantum gas dynamics

    International Nuclear Information System (INIS)

    Shi, Yu-Hsin; Huang, J.C.; Yang, J.Y.

    2007-01-01

    A class of high resolution kinetic beam schemes in multiple space dimensions in general coordinates system for the ideal quantum gas is presented for the computation of quantum gas dynamical flows. The kinetic Boltzmann equation approach is adopted and the local equilibrium quantum statistics distribution is assumed. High-order accurate methods using essentially non-oscillatory interpolation concept are constructed. Computations of shock wave diffraction by a circular cylinder in an ideal quantum gas are conducted to illustrate the present method. The present method provides a viable means to explore various practical ideal quantum gas flows

  7. Relevance and bio-catalytic strategies for the kinetic resolution of ketoprofen towards dexketoprofen.

    Science.gov (United States)

    Toledo, María Victoria; Briand, Laura Estefanía

    2017-11-10

    This review presents the most relevant investigations concerning the biocatalytic kinetic resolution of racemic ketoprofen to dexketoprofen for the last 22 years. The advantages related to the administration of the dex-enantiomer in terms of human health, the so called "chiral switch" in the pharmaceutical industry and the sustainability of biotransformations have been the driving forces to develop innovative technology to obtain dexketoprofen. In particular, the kinetic resolution of racemic ketoprofen through enantiomeric esterification and hydrolysis using lipases as biocatalysts are thoroughly revised and commented upon. In this context, the biocatalysts, acyl-acceptors (alcohols), reaction conditions, conversion, enantiomeric excess, and enantiomeric ratio among others are discussed. Moreover, the investigations concerning scaling up processes in order to obtain an optically pure enantiomer of the profen are presented. Finally, some guidelines about perspectives of the technology and research opportunities are given.

  8. Fluxionally chiral DMAP catalysts: kinetic resolution of axially chiral biaryl compounds.

    Science.gov (United States)

    Ma, Gaoyuan; Deng, Jun; Sibi, Mukund P

    2014-10-27

    Can organocatalysts that incorporate fluxional groups provide enhanced selectivity in asymmetric transformations? To address this issue, we have designed chiral 4-dimethylaminopyridine (DMAP) catalysts with fluxional chirality. These catalysts were found to be efficient in promoting the acylative kinetic resolution of secondary alcohols and axially chiral biaryl compounds with selectivity factors of up to 37 and 51, respectively. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Simplification of lipase design in the enzymatic kinetic resolution of amines by saturation transfer difference NMR

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Marcio S.; Pietrobom, Daniel, E-mail: s.marcio@ufabc.edu.br [Universidade Federal do ABC (CCNH/UFABC), Santo André, SP (Brazil). Centro de Ciências Naturais e Humanas

    2016-07-01

    In this work, we demonstrate a nuclear magnetic resonance (NMR) method for racemic amide and lipase interaction as a first-pass design method in the enzymatic kinetic resolution of amines. As a novel adaptation of commonly used protein-ligand screening NMR methodologies, this approach relies upon a lipase-amide interaction wherein the time-consuming is reduced drastically and new insights are produced during the development of biocatalysis reactions. (author)

  10. Lipase-catalyzed highly enantioselective kinetic resolution of boron-containing chiral alcohols.

    Science.gov (United States)

    Andrade, Leandro H; Barcellos, Thiago

    2009-07-16

    The first application of enzymes as catalysts to obtain optically pure boron compounds is described. The kinetic resolution of boron-containing chiral alcohols via enantioselective transesterification catalyzed by lipases was studied. Aromatic, allylic, and aliphatic secondary alcohols containing a boronate ester or boronic acid group were resolved by lipase from Candida antartica (CALB), and excellent E values (E > 200) and high enantiomeric excesses (up to >99%) of both remaining substrates and acetylated product were obtained.

  11. Kinetic and dynamic kinetic resolution of secondary alcohols with ionic-surfactant-coated Burkholderia cepacia lipase: substrate scope and enantioselectivity.

    Science.gov (United States)

    Kim, Cheolwoo; Lee, Jusuk; Cho, Jeonghun; Oh, Yeonock; Choi, Yoon Kyung; Choi, Eunjeong; Park, Jaiwook; Kim, Mahn-Joo

    2013-03-15

    Forty-four different secondary alcohols, which can be classified into several types (II-IX), were tested as the substrates of ionic surfactant-coated Burkholderia cepacia lipase (ISCBCL) to see its substrate scope and enantioselectivity in kinetic and dynamic kinetic resolution (KR and DKR). They include 6 boron-containing alcohols, 24 chiral propargyl alcohols, and 14 diarylmethanols. The results from the studies on KR indicate that ISCBCL accepted most of them with high enantioselectivity at ambient temperature and with useful to high enantioselectivity at elevated temperatures. In particular, ISCBCL displayed high enantioselectivity toward sterically demanding secondary alcohols (types VIII and IX) which have two bulky substituents at the hydroxymethine center. DKR reactions were performed by the combination of ISCBCL with a ruthenium-based racemization catalyst at 25-60 °C. Forty-one secondary alcohols were tested for DKR. About half of them were transformed into their acetates of high enantiopurity (>90% ee) with good yields (>80%). It is concluded that ISCBCL appears to be a superb enzyme for the KR and DKR of secondary alcohols.

  12. Microwave Assisted Enzymatic Kinetic Resolution of (±-1-Phenyl-2-propyn-1-ol in Nonaqueous Media

    Directory of Open Access Journals (Sweden)

    Saravanan Devendran

    2014-01-01

    Full Text Available Kinetic resolution of 1-phenyl-2-propyn-1-ol, an important chiral synthon, was studied through trans-esterification with acyl acetate to investigate synergism between microwave irradiation and enzyme catalysis. Lipases from different microbial origins were employed for the kinetic resolution of (R/S-1-phenyl-2-propyn-1-ol, among which Candida antarctica lipase B, immobilized on acrylic resin (Novozym 435, was found to be the best catalyst in n-hexane as solvent. Vinyl acetate was the most effective among different acyl esters studied. The effect of various parameters was studied in a systematic manner. Definite synergism between microwave and enzyme was observed. The initial rate was improved around 1.28 times under microwave irradiation than conventional heating. Under optimum conditions, maximum conversion (48.78% and high enantiomeric excess (93.25% were obtained in 2 h. From modeling studies, it is concluded that the reaction follows the Ping-Pong bi-bi mechanism with dead end alcohol inhibition. Kinetic parameters were obtained by using nonlinear regression. This process is green, clean, and easily scalable as compared to the chemical process.

  13. Canceling effect leads temperature insensitivity of hydrolytic enzymes in soil

    Science.gov (United States)

    Razavi, Bahar S.; Blagodatskaya, Evgenia; Kuzyakov, Yakov

    2015-04-01

    microorganisms in soil at these temperature ranges. We conclude that the temperature sensitivity (Q10) of enzyme activity declines at higher temperature and lower concentration of substrates in soil. Overall, our results suggest that the fine-scale (five degree) temperature resolution level needs to be considered in global earth system models especially at temperature thresholds for physiological groups of soil microorganisms. Refcences: Allison, S.D., Wallenstein, M.D., Bradford, M.A., 2010. Soil-carbon response to warming dependent on microbial physiology. Nat. Geosci. 3, 336-340. doi:10.1038/ngeo846 Chen, R., Blagodatskaya, E., Senbayram, M., Blagodatsky, S., Myachina, O., Dittert, K., Kuzyakov, Y., 2012. Decomposition of biogas residues in soil and their effects on microbial growth kinetics and enzyme activities. Biomass Bioenergy 45, 221-229. doi:10.1016/j.biombioe.2012.06.014 German, D.P., Weintraub, M.N., Grandy, A.S., Lauber, C.L., Rinkes, Z.L., Allison, S.D., 2011. Optimization of hydrolytic and oxidative enzyme methods for ecosystem studies. Soil Biol. Biochem. 43, 1387-1397. doi:10.1016/j.soilbio.2011.03.017

  14. Kinetic resolution and stereoselective synthesis of 3-substituted aspartic acids by using engineered methylaspartate ammonia lyases.

    Science.gov (United States)

    Raj, Hans; Szymanski, Wiktor; de Villiers, Jandré; Puthan Veetil, Vinod; Quax, Wim J; Shimamoto, Keiko; Janssen, Dick B; Feringa, Ben L; Poelarends, Gerrit J

    2013-08-19

    Enzymatic amino acid synthesis: Kinetic resolution and asymmetric synthesis of various valuable 3-substituted aspartic acids, which were obtained in fair to good yields with diastereomeric ratio values of up to >98:2 and enantiomeric excess values of up to >99 %, by using engineered methylaspartate ammonia lyases are described. These biocatalytic methodologies for the selective preparation of aspartic acid derivatives appear to be attractive alternatives for existing chemical methods. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    KAUST Repository

    Ebner, Davidâ C.

    2009-12-07

    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  16. Large-scale ruthenium- and enzyme-catalyzed dynamic kinetic resolution of (rac-1-phenylethanol

    Directory of Open Access Journals (Sweden)

    Bäckvall Jan-E

    2007-12-01

    Full Text Available Abstract The scale-up of the ruthenium- and enzyme-catalyzed dynamic kinetic resolution (DKR of (rac-1-phenylethanol (2 is addressed. The immobilized lipase Candida antarctica lipase B (CALB was employed for the resolution, which shows high enantioselectivity in the transesterification. The ruthenium catalyst used, (η 5-C5Ph5RuCl(CO2 1, was shown to possess very high reactivity in the "in situ" redox racemization of 1-phenylethanol (2 in the presence of the immobilized enzyme, and could be used in 0.05 mol% with high efficiency. Commercially available isopropenyl acetate was employed as acylating agent in the lipase-catalyzed transesterifications, which makes the purification of the product very easy. In a successful large-scale DKR of 2, with 0.05 mol% of 1, (R-1-phenylethanol acetate (3 was obtained in 159 g (97% yield in excellent enantiomeric excess (99.8% ee.

  17. The Palladium-Catalyzed Aerobic Kinetic Resolution of Secondary Alcohols: Reaction Development, Scope, and Applications

    KAUST Repository

    Ebner, Davidâ C.; Bagdanoff, Jeffreyâ T.; Ferreira, Ericâ M.; McFadden, Ryanâ M.; Caspi, Danielâ D.; Trend, Raissaâ M.; Stoltz, Brianâ M.

    2009-01-01

    The first palladium-catalyzed enantioselective oxidation of secondary alcohols has been developed, utilizing the readily available diamine (-)-sparteine as a chiral ligand and molecular oxygen as the stoichiometric oxidant. Mechanistic insights regarding the role of the base and hydrogen-bond donors have resulted in several improvements to the original system. Namely, addition of cesium carbonate and tert-butyl alcohol greatly enhances reaction rates, promoting rapid resolutions. The use of chloroform as solvent allows the use of ambient air as the terminal oxidant at 23 degrees C, resulting in enhanced catalyst selectivity. These improved reaction conditions have permitted the successful kinetic resolution of benzylic, allylic, and cyclopropyl secondary alcohols to high enantiomeric excess with good-to-excellent selectivity factors. This catalyst system has also been applied to the desymmetrization of meso-diols, providing high yields of enantioenriched hydroxyketones.

  18. Multi-scale method for the resolution of the neutronic kinetics equations

    International Nuclear Information System (INIS)

    Chauvet, St.

    2008-10-01

    In this PhD thesis and in order to improve the time/precision ratio of the numerical simulation calculations, we investigate multi-scale techniques for the resolution of the reactor kinetics equations. We choose to focus on the mixed dual diffusion approximation and the quasi-static methods. We introduce a space dependency for the amplitude function which only depends on the time variable in the standard quasi-static context. With this new factorization, we develop two mixed dual problems which can be solved with Cea's solver MINOS. An algorithm is implemented, performing the resolution of these problems defined on different scales (for time and space). We name this approach: the Local Quasi-Static method. We present here this new multi-scale approach and its implementation. The inherent details of amplitude and shape treatments are discussed and justified. Results and performances, compared to MINOS, are studied. They illustrate the improvement on the time/precision ratio for kinetics calculations. Furthermore, we open some new possibilities to parallelize computations with MINOS. For the future, we also introduce some improvement tracks with adaptive scales. (author)

  19. Zymography methods for visualizing hydrolytic enzymes

    OpenAIRE

    Vandooren, Jennifer; Geurts, Nathalie; Martens, Erik; Van den Steen, Philippe E.; Opdenakker, Ghislain

    2013-01-01

    Zymography is a technique for studying hydrolytic enzymes on the basis of substrate degradation. It is a powerful., but often misinterpreted, tool. yielding information on potential. hydrolytic activities, enzyme forms and the locations of active enzymes. In this Review, zymography techniques are compared in terms of advantages, limitations and interpretations. With in gel zymography, enzyme forms are visualized according to their molecular weights. Proteolytic activities are localized in tis...

  20. Development of dynamic kinetic resolution on large scale for (±-1-phenylethylamine

    Directory of Open Access Journals (Sweden)

    Lisa K. Thalén

    2010-09-01

    Full Text Available Candida antarctica lipase B (CALB and racemization catalyst 4 were combined in the dynamic kinetic resolution (DKR of (±-1-phenylethylamine (1. Several reaction parameters have been investigated to modify the method for application on multigram scale. A comparison of isopropyl acetate and alkyl methoxyacetates as acyl donors was carried out. It was found that lower catalyst loadings could be used to obtain (R-2-methoxy-N-(1-phenylethylacetamide (3 in good yield and high ee when alkyl methoxyacetates were used as acyl donors compared to when isopropyl acetate was used as the acyl donor. The catalyst loading could be decreased to 1.25 mol % Ru-catalyst 4 and 10 mg CALB per mmol 1 when alkyl methoxyacetates were used as the acyl donor.

  1. Development of dynamic kinetic resolution on large scale for (±)-1-phenylethylamine.

    Science.gov (United States)

    Thalén, Lisa K; Bäckvall, Jan-E

    2010-09-13

    Candida antarctica lipase B (CALB) and racemization catalyst 4 were combined in the dynamic kinetic resolution (DKR) of (±)-1-phenylethylamine (1). Several reaction parameters have been investigated to modify the method for application on multigram scale. A comparison of isopropyl acetate and alkyl methoxyacetates as acyl donors was carried out. It was found that lower catalyst loadings could be used to obtain (R)-2-methoxy-N-(1-phenylethyl)acetamide (3) in good yield and high ee when alkyl methoxyacetates were used as acyl donors compared to when isopropyl acetate was used as the acyl donor. The catalyst loading could be decreased to 1.25 mol % Ru-catalyst 4 and 10 mg CALB per mmol 1 when alkyl methoxyacetates were used as the acyl donor.

  2. Chemoenzymatic dynamic kinetic resolution of primary amines using a recyclable palladium nanoparticle catalyst together with lipases.

    Science.gov (United States)

    Gustafson, Karl P J; Lihammar, Richard; Verho, Oscar; Engström, Karin; Bäckvall, Jan-E

    2014-05-02

    A catalyst consisting of palladium nanoparticles supported on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was used in chemoenzymatic dynamic kinetic resolution (DKR) to convert primary amines to amides in high yields and excellent ee's. The efficiency of the nanocatalyst at temperatures below 70 °C enables reaction conditions that are more suitable for enzymes. In the present study, this is exemplified by subjecting 1-phenylethylamine (1a) and analogous benzylic amines to DKR reactions using two commercially available lipases, Novozyme-435 (Candida antartica Lipase B) and Amano Lipase PS-C1 (lipase from Burkholderia cepacia) as biocatalysts. The latter enzyme has not previously been used in the DKR of amines because of its low stability at temperatures over 60 °C. The viability of the heterogeneous Pd-AmP-MCF was further demonstrated in a recycling study, which shows that the catalyst can be reused up to five times.

  3. Recent Advances in Dynamic Kinetic Resolution by Chiral Bifunctional (Thio)urea- and Squaramide-Based Organocatalysts.

    Science.gov (United States)

    Li, Pan; Hu, Xinquan; Dong, Xiu-Qin; Zhang, Xumu

    2016-10-14

    The organocatalysis-based dynamic kinetic resolution (DKR) process has proved to be a powerful strategy for the construction of chiral compounds. In this feature review, we summarized recent progress on the DKR process, which was promoted by chiral bifunctional (thio)urea and squaramide catalysis via hydrogen-bonding interactions between substrates and catalysts. A wide range of asymmetric reactions involving DKR, such as asymmetric alcoholysis of azlactones, asymmetric Michael-Michael cascade reaction, and enantioselective selenocyclization, are reviewed and demonstrate the efficiency of this strategy. The (thio)urea and squaramide catalysts with dual activation would be efficient for more unmet challenges in dynamic kinetic resolution.

  4. Energy resolution and efficiency of phonon-mediated kinetic inductance detectors for light detection

    International Nuclear Information System (INIS)

    Cardani, L.; Colantoni, I.; Coppolecchia, A.; Cruciani, A.; Vignati, M.; Bellini, F.; Casali, N.; Cosmelli, C.; Di Domizio, S.; Castellano, M. G.; Tomei, C.

    2015-01-01

    The development of sensitive cryogenic light detectors is of primary interest for bolometric experiments searching for rare events like dark matter interactions or neutrino-less double beta decay. Thanks to their good energy resolution and the natural multiplexed read-out, Kinetic Inductance Detectors (KIDs) are particularly suitable for this purpose. To efficiently couple KIDs-based light detectors to the large crystals used by the most advanced bolometric detectors, active surfaces of several cm 2 are needed. For this reason, we are developing phonon-mediated detectors. In this paper, we present the results obtained with a prototype consisting of four 40 nm thick aluminum resonators patterned on a 2 × 2 cm 2 silicon chip, and calibrated with optical pulses and X-rays. The detector features a noise resolution σ E  = 154 ± 7 eV and an (18 ± 2)% efficiency

  5. Energy resolution and efficiency of phonon-mediated kinetic inductance detectors for light detection

    Energy Technology Data Exchange (ETDEWEB)

    Cardani, L., E-mail: laura.cardani@roma1.infn.it [Dipartimento di Fisica, Sapienza Università di Roma, Piazzale Aldo Moro 2, 00185 Roma (Italy); Physics Department, Princeton University, Washington Road, 08544, Princeton, New Jersey (United States); Colantoni, I.; Coppolecchia, A. [Dipartimento di Fisica, Sapienza Università di Roma, Piazzale Aldo Moro 2, 00185 Roma (Italy); Cruciani, A.; Vignati, M.; Bellini, F.; Casali, N.; Cosmelli, C. [Dipartimento di Fisica, Sapienza Università di Roma, Piazzale Aldo Moro 2, 00185 Roma (Italy); INFN - Sezione di Roma, Piazzale Aldo Moro 2, 00185 Roma (Italy); Di Domizio, S. [Dipartimento di Fisica, Università degli Studi di Genova, Via Dodecaneso 33, 16146 Genova (Italy); INFN - Sezione di Genova, Via Dodecaneso 33, 16146 Genova (Italy); Castellano, M. G. [Istituto di Fotonica e Nanotecnologie - CNR, Via Cineto Romano 42, 00156 Roma (Italy); Tomei, C. [INFN - Sezione di Roma, Piazzale Aldo Moro 2, 00185 Roma (Italy)

    2015-08-31

    The development of sensitive cryogenic light detectors is of primary interest for bolometric experiments searching for rare events like dark matter interactions or neutrino-less double beta decay. Thanks to their good energy resolution and the natural multiplexed read-out, Kinetic Inductance Detectors (KIDs) are particularly suitable for this purpose. To efficiently couple KIDs-based light detectors to the large crystals used by the most advanced bolometric detectors, active surfaces of several cm{sup 2} are needed. For this reason, we are developing phonon-mediated detectors. In this paper, we present the results obtained with a prototype consisting of four 40 nm thick aluminum resonators patterned on a 2 × 2 cm{sup 2} silicon chip, and calibrated with optical pulses and X-rays. The detector features a noise resolution σ{sub E} = 154 ± 7 eV and an (18 ± 2)% efficiency.

  6. Hydrolytic enzyme activity enhanced by Barium supplementation

    Directory of Open Access Journals (Sweden)

    Camilo Muñoz

    2016-10-01

    Full Text Available Hydrolysis of polymers is a first and often limiting step during the degradation of plant residues. Plant biomass is generally a major component of waste residues and a major renewable resource to obtain a variety of secondary products including biofuels. Improving the performance of enzymatic hydrolysis of plant material with minimum costs and limiting the use of additional microbial biomass or hydrolytic enzymes directly influences competitiveness of these green biotechnological processes. In this study, we cloned and expressed a cellulase and two esterases recovered from environmental thermophilic soil bacterial communities and characterize their optimum activity conditions including the effect of several metal ions. Results showed that supplementing these hydrolytic reactions with Barium increases the activity of these extracellular hydrolytic enzymes. This observation represents a simple but major improvement to enhance the efficiency and competitiveness of this process within an increasingly important biotechnological sector.

  7. Zymography methods for visualizing hydrolytic enzymes.

    Science.gov (United States)

    Vandooren, Jennifer; Geurts, Nathalie; Martens, Erik; Van den Steen, Philippe E; Opdenakker, Ghislain

    2013-03-01

    Zymography is a technique for studying hydrolytic enzymes on the basis of substrate degradation. It is a powerful, but often misinterpreted, tool yielding information on potential hydrolytic activities, enzyme forms and the locations of active enzymes. In this Review, zymography techniques are compared in terms of advantages, limitations and interpretations. With in gel zymography, enzyme forms are visualized according to their molecular weights. Proteolytic activities are localized in tissue sections with in situ zymography. In vivo zymography can pinpoint proteolytic activity to sites in an intact organism. Future development of novel substrate probes and improvement in detection and imaging methods will increase the applicability of zymography for (reverse) degradomics studies.

  8. Flow chemistry and polymer-supported pseudoenantiomeric acylating agents enable parallel kinetic resolution of chiral saturated N-heterocycles

    Science.gov (United States)

    Kreituss, Imants; Bode, Jeffrey W.

    2017-05-01

    Kinetic resolution is a common method to obtain enantioenriched material from a racemic mixture. This process will deliver enantiopure unreacted material when the selectivity factor of the process, s, is greater than 1; however, the scalemic reaction product is often discarded. Parallel kinetic resolution, on the other hand, provides access to two enantioenriched products from a single racemic starting material, but suffers from a variety of practical challenges regarding experimental design that limit its applications. Here, we describe the development of a flow-based system that enables practical parallel kinetic resolution of saturated N-heterocycles. This process provides access to both enantiomers of the starting material in good yield and high enantiopurity; similar results with classical kinetic resolution would require selectivity factors in the range of s = 100. To achieve this, two immobilized quasienantiomeric acylating agents were designed for the asymmetric acylation of racemic saturated N-heterocycles. Using the flow-based system we could efficiently separate, recover and reuse the polymer-supported reagents. The amide products could be readily separated and hydrolysed to the corresponding amines without detectable epimerization.

  9. Kinetic Resolution of sec-Thiols via Enantioselective Oxidation with Rationally Engineered 5-(Hydroxymethyl)furfural Oxidase

    NARCIS (Netherlands)

    Pickl, Mathias; Swoboda, Alexander; Romero, Elvira; Winkler, Christoph; Binda, Claudia; Mattevi, Andrea; Faber, Kurt; Fraaije, Marco

    2018-01-01

    Various flavoprotein oxidases were recently shown to oxidize prim-thiols. Here we extend this reactivity towards sec-thiols via structure-guided engineering of 5-(hydroxymethyl)furfural oxidase (HMFO). The variants obtained were employed for the oxidative kinetic resolution of rac-sec-thiols

  10. Kinetic resolution of α-bromoamides: Experimental and theoretical investigation of highly enantioselective reactions catalyzed by haloalkane dehalogenases

    NARCIS (Netherlands)

    Westerbeek, Alja; Szymanski, Wiktor; Wijma, Hein J.; Marrink, Siewert; Feringa, Ben L.; Janssen, Dick B.

    2011-01-01

    Haloalkane dehalogenases from five sources were heterologously expressed in Escherichia coli, isolated, and tested for their ability to achieve kinetic resolution of racemic alpha-bromoamides, which are important intermediates used in the preparation of bioactive compounds. To explore the substrate

  11. Resolution of the diffusional paradox predicting infinitely fast kinetics on the nanoscale

    Science.gov (United States)

    Beke, D. L.; Erdélyi, Z.

    2006-01-01

    In our paper, we offer a natural resolution for a long-standing paradox in diffusion. We show that the growth rate of the diffusion zone (reaction layer) should not go to infinity with decreasing time (as 1/t ), just because the diffusion permeability of the interface is finite. Expression for the changeover thickness X* between the linear and parabolic regimes of the interface shift in phase separating binary A(B) systems is derived in the framework of a deterministic atomistic model for diffusion. X* lies typically between 0.01 and 300nm , depending on the composition dependence of the diffusion coefficient and the phase separation tendency of the alloy. While in ideal binary alloys with composition independent diffusivity, the deviation from the parabolic law practically cannot be observed, in real systems (where the diffusion coefficient can change several orders of magnitude with the composition), measurable deviations are expected as it was experimentally observed very recently in the Ni/Cu and Au/Ni systems. We also offer an atomistic explanation for the phenomenological interface transfer coefficient K . It measures the finite interface permeability (proportional to the jump frequency across the interface) and thus it controls the shift of the interface at short times (diffusion distances). Although it is almost exclusively accepted in the literature that linear growth kinetics are the result of interface reaction control, our results suggest that the linear or nonparabolic growth of a reaction layer on the nanoscale cannot be automatically interpreted by an interface reaction.

  12. MOLECULAR DYNAMICS SIMULATION OF KINETIC RESOLUTION OF RACEMIC ALCOHOL USING BURKHOLDERIA CEPACIA LIPASE IN ORGANIC SOLVENTS

    Directory of Open Access Journals (Sweden)

    A. C. Mathpati

    2018-03-01

    Full Text Available Lipases, a subclass of hydrolases, have gained a lot of importance as they can catalyze esterification, transesterification and hydrolysis reaction in non-aqueous media. Lipases are also widely used for kinetic resolution of racemic alcohols into enantiopure compounds. The lipase activity is affected by organic solvents due to changes in the conformational rigidity of enzymes, the active site, or altering the solvation of the transition state. The activity of lipases strongly depends on the logP value of solvents. Molecular dynamics (MD can help to understand the effect of solvents on lipase conformation as well as protein-ligand complex. In this work, MD simulations of Burkholderia cepacia lipase (BCL and complex between R and S conformation of acetylated form of 1-phenylethanol with BCL using gromacs have been carried in various organic solvents. The RMSD values were within the range of 0.15 to 0.20 nm and radius of gyration was found to be with 1.65 to 1.9 nm. Major changes in the B factor compared to reference structure were observed between residues 60 to 80, 120 to 150 and 240 to 260. Higher unfolding was observed in toluene and diethyl ether compared to hexane and acetonitrile. R acetylated complex was found to favorably bind BCL compared to S form. The predicted enantioselectivity were in good agreement with the experimental data.

  13. Chemoenzymatic Dynamic Kinetic Resolution: A Powerful Tool for the Preparation of Enantiomerically Pure Alcohols and Amines

    Science.gov (United States)

    2015-01-01

    Chemoenzymatic dynamic kinetic resolution (DKR) constitutes a convenient and efficient method to access enantiomerically pure alcohol and amine derivatives. This Perspective highlights the work carried out within this field during the past two decades and pinpoints important avenues for future research. First, the Perspective will summarize the more developed area of alcohol DKR, by delineating the way from the earliest proof-of-concept protocols to the current state-of-the-art systems that allows for the highly efficient and selective preparation of a wide range of enantiomerically pure alcohol derivatives. Thereafter, the Perspective will focus on the more challenging DKR of amines, by presenting the currently available homogeneous and heterogeneous methods and their respective limitations. In these two parts, significant attention will be dedicated to the design of efficient racemization methods as an important means of developing milder DKR protocols. In the final part of the Perspective, a brief overview of the research that has been devoted toward improving enzymes as biocatalysts is presented. PMID:25730714

  14. Merging Iron Catalysis and Biocatalysis-Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

    KAUST Repository

    El-Sepelgy, Osama

    2016-09-29

    A dual catalytic iron/lipase system has been developed and applied in the dynamic kinetic resolution of benzylic and aliphatic secondary alcohols. A detailed study of the Knölker-type iron complexes demonstrated the hydrogen autotransfer of alcohols to proceed under mild reaction conditions and allowed the combination with the enzymatic resolution. Different racemic alcohols were efficiently converted to chiral acetates in good yields and with excellent enantioselectivities. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

  15. Merging Iron Catalysis and Biocatalysis-Iron Carbonyl Complexes as Efficient Hydrogen Autotransfer Catalysts in Dynamic Kinetic Resolutions

    KAUST Repository

    El-Sepelgy, Osama; Alandini, Nurtalya; Rueping, Magnus

    2016-01-01

    A dual catalytic iron/lipase system has been developed and applied in the dynamic kinetic resolution of benzylic and aliphatic secondary alcohols. A detailed study of the Knölker-type iron complexes demonstrated the hydrogen autotransfer of alcohols to proceed under mild reaction conditions and allowed the combination with the enzymatic resolution. Different racemic alcohols were efficiently converted to chiral acetates in good yields and with excellent enantioselectivities. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

  16. The Hydrolytic Stability and Degradation Mechanism of a Hierarchically Porous Metal Alkylphosphonate Framework

    Directory of Open Access Journals (Sweden)

    Kai Lv

    2018-03-01

    Full Text Available To aid the design of a hierarchically porous unconventional metal-phosphonate framework (HP-UMPF for practical radioanalytical separation, a systematic investigation of the hydrolytic stability of bulk phase against acidic corrosion has been carried out for an archetypical HP-UMPF. Bulk dissolution results suggest that aqueous acidity has a more paramount effect on incongruent leaching than the temperature, and the kinetic stability reaches equilibrium by way of an accumulation of a partial leached species on the corrosion conduits. A variation of particle morphology, hierarchical porosity and backbone composition upon corrosion reveals that they are hydrolytically resilient without suffering any great degradation of porous texture, although large aggregates crack into sporadic fractures while the nucleophilic attack of inorganic layers cause the leaching of tin and phosphorus. The remaining selectivity of these HP-UMPFs is dictated by a balance between the elimination of free phosphonate and the exposure of confined phosphonates, thus allowing a real-time tailor of radionuclide sequestration. Moreover, a plausible degradation mechanism has been proposed for the triple progressive dissolution of three-level hierarchical porous structures to elucidate resultant reactivity. These HP-UMPFs are compared with benchmark metal-organic frameworks (MOFs to obtain a rough grading of hydrolytic stability and two feasible approaches are suggested for enhancing their hydrolytic stability that are intended for real-life separation protocols.

  17. Iron oxide nanoparticle-based magnetic resonance method to monitor release kinetics from polymeric particles with high resolution.

    Science.gov (United States)

    Chan, Minnie; Schopf, Eric; Sankaranarayanan, Jagadis; Almutairi, Adah

    2012-09-18

    A new method to precisely monitor rapid release kinetics from polymeric particles using super paramagnetic iron oxide nanoparticles, specifically by measuring spin-spin relaxation time (T(2)), is reported. Previously, we have published the formulation of logic gate particles from an acid-sensitive poly-β-aminoester ketal-2 polymer. Here, a series of poly-β-aminoester ketal-2 polymers with varying hydrophobicities were synthesized and used to formulate particles. We attempted to measure fluorescence of released Nile red to determine whether the structural adjustments could finely tune the release kinetics in the range of minutes to hours; however, this standard technique did not differentiate each release rate of our series. Thus, a new method based on encapsulation of iron oxide nanoparticles was developed, which enabled us to resolve the release kinetics of our particles. Moreover, the kinetics matched the relative hydrophobicity order determined by octanol-water partition coefficients. To the best of our knowledge, this method provides the highest resolution of release kinetics to date.

  18. A model for hydrolytic degradation and erosion of biodegradable polymers.

    Science.gov (United States)

    Sevim, Kevser; Pan, Jingzhe

    2018-01-15

    For aliphatic polyesters such as PLAs and PGAs, there is a strong interplay between the hydrolytic degradation and erosion - degradation leads to a critically low molecular weight at which erosion starts. This paper considers the underlying physical and chemical processes of hydrolytic degradation and erosion. Several kinetic mechanisms are incorporated into a mathematical model in an attempt to explain different behaviours of mass loss observed in experiments. In the combined model, autocatalytic hydrolysis, oligomer production and their diffusion are considered together with surface and interior erosion using a set of differential equations and Monte Carlo technique. Oligomer and drug diffusion are modelled using Fick's law with the diffusion coefficients dependent on porosity. The porosity is due to the formation of cavities which are a result of polymer erosion. The model can follow mass loss and drug release up to 100%, which cannot be explained using a simple reaction-diffusion. The model is applied to two case studies from the literature to demonstrate its validity. The case studies show that a critical molecular weight for the onset of polymer erosion and an incubation period for the polymer dissolution are two critical factors that need to be considered when predicting mass loss and drug release. In order to design bioresorbable implants, it is important to have a mathematical model to predict polymer degradation and corresponding drug release. However, very different behaviours of polymer degradation have been observed and there is no single model that can capture all these behaviours. For the first time, the model presented in this paper is capable of capture all these observed behaviours by switching on and off different underlying mechanisms. Unlike the existing reaction-diffusion models, the model presented here can follow the degradation and drug release all the way to the full disappearance of an implant. Crown Copyright © 2017. Published by

  19. Stereoselective Preparation of N-Alkyl Dipeptide Analogues via Dynamic Kinetic Resolution of α-Halo Acyl Amino Esters

    International Nuclear Information System (INIS)

    Shin, Eun Kyoung; Chang, Ji Yeon; Kim, Hyun Jung; Kim, Yong Tae; Park, Yong Sun

    2006-01-01

    We have shown that dynamic kinetic resolution of α-bromo and α-chloro amides in nucleophilic substitution reaction can be successfully applied towards the preparation of various N-terminal functionalized dipeptide analogues. The stereochemical aspects of the results showed that stereoselectivity depends critically on the structures of amine nucleophiles. This mild and practical method can be run on a multi-gram scale without any special precautions and should be applicable to stereoselective syntheses of various peptidomimetics. Extension of this synthetic methodology to dynamic resolution of N-(α-haloacetyl) peptides in the stereospecific nucleophilic substitution (S N 2) could be an attractive synthetic strategy for asymmetric syntheses of peptide analogues. Recently it has been shown from our group that the chiral information of adjacent amino acid residue is efficiently transferred to the new C-N bond formation at α-halo carbon center for asymmetric syntheses of di-, tri- and tetrapeptide analogues. The α-halo stereogenic center of undergoes rapid epimerization in the presence of diisopropylethylamine (DIEA) and tetrabutylammonium iodide (TBAI), and (αS) reacts with the nucleophile preferentially to provide the dipeptide analogue (αR). The mechanistic investigation showed that this is a case of dynamic kinetic resolution, in which the stereoselectivity is determined by the difference in the diastereomeric transition state energies for the reaction with the nucleophiles. Herein we describe our recent progress to extend the scope of the methodology to stereoselective preparation of N-terminal functionalized dipeptide analogues with various amine nucleophiles

  20. Measuring Absolute RNA Copy Numbers at High Temporal Resolution Reveals Transcriptome Kinetics in Development

    Directory of Open Access Journals (Sweden)

    Nick D.L. Owens

    2016-01-01

    Full Text Available Transcript regulation is essential for cell function, and misregulation can lead to disease. Despite technologies to survey the transcriptome, we lack a comprehensive understanding of transcript kinetics, which limits quantitative biology. This is an acute challenge in embryonic development, where rapid changes in gene expression dictate cell fate decisions. By ultra-high-frequency sampling of Xenopus embryos and absolute normalization of sequence reads, we present smooth gene expression trajectories in absolute transcript numbers. During a developmental period approximating the first 8 weeks of human gestation, transcript kinetics vary by eight orders of magnitude. Ordering genes by expression dynamics, we find that “temporal synexpression” predicts common gene function. Remarkably, a single parameter, the characteristic timescale, can classify transcript kinetics globally and distinguish genes regulating development from those involved in cellular metabolism. Overall, our analysis provides unprecedented insight into the reorganization of maternal and embryonic transcripts and redefines our ability to perform quantitative biology.

  1. Palladium-Catalyzed Enantioselective C-H Olefination of Diaryl Sulfoxides through Parallel Kinetic Resolution and Desymmetrization.

    Science.gov (United States)

    Zhu, Yu-Chao; Li, Yan; Zhang, Bo-Chao; Zhang, Feng-Xu; Yang, Yi-Nuo; Wang, Xi-Sheng

    2018-03-07

    The first example of Pd II -catalyzed enantioselective C-H olefination with non-chiral or racemic sulfoxides as directing groups was developed. A variety of chiral diaryl sulfoxides were synthesized with high enantioselectivity (up to 99 %) through both desymmetrization and parallel kinetic resolution (PKR). This is the first report of Pd II -catalyzed enantioselective C(sp 2 )-H functionalization through PKR, and it represents a novel strategy to construct sulfur chiral centers. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. A quenched-flow system for measuring heterogeneous enzyme kinetics with sub-second time resolution

    DEFF Research Database (Denmark)

    Olsen, Johan Pelck; Kari, Jeppe; Borch, Kim

    2017-01-01

    of insoluble substrate. Perhaps for this reason, transient kinetics has rarely been reported for heterogeneous enzyme reactions. Here, we describe a quenched-flow system using peristaltic pumps and stirred substrate suspensions with a dead time below 100 ms. The general performance was verified by alkali...

  3. High-resolution Statistics of Solar Wind Turbulence at Kinetic Scales Using the Magnetospheric Multiscale Mission

    Energy Technology Data Exchange (ETDEWEB)

    Chasapis, Alexandros; Matthaeus, W. H.; Parashar, T. N.; Maruca, B. A. [University of Delaware, Newark, DE (United States); Fuselier, S. A.; Burch, J. L. [Southwest Research Institute, San Antonio, TX (United States); Phan, T. D. [Space Sciences Laboratory, University of California, Berkeley, CA (United States); Moore, T. E.; Pollock, C. J.; Gershman, D. J. [NASA Goddard Space Flight Center, Greenbelt, MD (United States); Torbert, R. B. [University of New Hampshire, Durham, NH (United States); Russell, C. T.; Strangeway, R. J., E-mail: chasapis@udel.edu [University of California, Los Angeles, CA (United States)

    2017-07-20

    Using data from the Magnetospheric Multiscale (MMS) and Cluster missions obtained in the solar wind, we examine second-order and fourth-order structure functions at varying spatial lags normalized to ion inertial scales. The analysis includes direct two-spacecraft results and single-spacecraft results employing the familiar Taylor frozen-in flow approximation. Several familiar statistical results, including the spectral distribution of energy, and the sale-dependent kurtosis, are extended down to unprecedented spatial scales of ∼6 km, approaching electron scales. The Taylor approximation is also confirmed at those small scales, although small deviations are present in the kinetic range. The kurtosis is seen to attain very high values at sub-proton scales, supporting the previously reported suggestion that monofractal behavior may be due to high-frequency plasma waves at kinetic scales.

  4. Hydrolytic catalysis and structural stabilization in a designed metalloprotein

    Science.gov (United States)

    Zastrow, Melissa L.; Peacock, Anna F. A.; Stuckey, Jeanne A.; Pecoraro, Vincent L.

    2011-01-01

    Metal ions are an important part of many natural proteins, providing structural, catalytic and electron transfer functions. Reproducing these functions in a designed protein is the ultimate challenge to our understanding of them. Here, we present an artificial metallohydrolase, which has been shown by X-ray crystallography to contain two different metal ions – a Zn(II) ion which is important for catalytic activity and a Hg(II) ion which provides structural stability. This metallohydrolase displays catalytic activity that compares well with several characteristic reactions of natural enzymes. It catalyses p-nitrophenyl acetate hydrolysis (pNPA) to within ~100-fold of the efficiency of human carbonic anhydrase (CA)II and is at least 550-fold better than comparable synthetic complexes. Similarly, CO2 hydration occurs with an efficiency within ~500-fold of CAII. While histidine residues in the absence of Zn(II) exhibit pNPA hydrolysis, miniscule apopeptide activity is observed for CO2 hydration. The kinetic and structural analysis of this first de novo designed hydrolytic metalloenzyme uncovers necessary design features for future metalloenzymes containing one or more metals. PMID:22270627

  5. Modeling Photo-Bleaching Kinetics to Create High Resolution Maps of Rod Rhodopsin in the Human Retina.

    Directory of Open Access Journals (Sweden)

    Martin Ehler

    Full Text Available We introduce and describe a novel non-invasive in-vivo method for mapping local rod rhodopsin distribution in the human retina over a 30-degree field. Our approach is based on analyzing the brightening of detected lipofuscin autofluorescence within small pixel clusters in registered imaging sequences taken with a commercial 488nm confocal scanning laser ophthalmoscope (cSLO over a 1 minute period. We modeled the kinetics of rhodopsin bleaching by applying variational optimization techniques from applied mathematics. The physical model and the numerical analysis with its implementation are outlined in detail. This new technique enables the creation of spatial maps of the retinal rhodopsin and retinal pigment epithelium (RPE bisretinoid distribution with an ≈ 50μm resolution.

  6. Modeling Photo-Bleaching Kinetics to Create High Resolution Maps of Rod Rhodopsin in the Human Retina

    Science.gov (United States)

    Ehler, Martin; Dobrosotskaya, Julia; Cunningham, Denise; Wong, Wai T.; Chew, Emily Y.; Czaja, Wojtek; Bonner, Robert F.

    2015-01-01

    We introduce and describe a novel non-invasive in-vivo method for mapping local rod rhodopsin distribution in the human retina over a 30-degree field. Our approach is based on analyzing the brightening of detected lipofuscin autofluorescence within small pixel clusters in registered imaging sequences taken with a commercial 488nm confocal scanning laser ophthalmoscope (cSLO) over a 1 minute period. We modeled the kinetics of rhodopsin bleaching by applying variational optimization techniques from applied mathematics. The physical model and the numerical analysis with its implementation are outlined in detail. This new technique enables the creation of spatial maps of the retinal rhodopsin and retinal pigment epithelium (RPE) bisretinoid distribution with an ≈ 50μm resolution. PMID:26196397

  7. Kinetic Resolution of sec-Thiols by Enantioselective Oxidation with Rationally Engineered 5-(Hydroxymethyl)furfural Oxidase.

    Science.gov (United States)

    Pickl, Mathias; Swoboda, Alexander; Romero, Elvira; Winkler, Christoph K; Binda, Claudia; Mattevi, Andrea; Faber, Kurt; Fraaije, Marco W

    2018-03-05

    Various flavoprotein oxidases were recently shown to oxidize primary thiols. Herein, this reactivity is extended to sec-thiols by using structure-guided engineering of 5-(hydroxymethyl)furfural oxidase (HMFO). The variants obtained were employed for the oxidative kinetic resolution of racemic sec-thiols, thus yielding the corresponding thioketones and nonreacted R-configured thiols with excellent enantioselectivities (E≥200). The engineering strategy applied went beyond the classic approach of replacing bulky amino acid residues with smaller ones, as the active site was additionally enlarged by a newly introduced Thr residue. This residue established a hydrogen-bonding interaction with the substrates, as verified in the crystal structure of the variant. These strategies unlocked HMFO variants for the enantioselective oxidation of a range of sec-thiols. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Novel approaches to estimating the turbulent kinetic energy dissipation rate from low- and moderate-resolution velocity fluctuation time series

    Directory of Open Access Journals (Sweden)

    M. Wacławczyk

    2017-11-01

    Full Text Available In this paper we propose two approaches to estimating the turbulent kinetic energy (TKE dissipation rate, based on the zero-crossing method by Sreenivasan et al. (1983. The original formulation requires a fine resolution of the measured signal, down to the smallest dissipative scales. However, due to finite sampling frequency, as well as measurement errors, velocity time series obtained from airborne experiments are characterized by the presence of effective spectral cutoffs. In contrast to the original formulation the new approaches are suitable for use with signals originating from airborne experiments. The suitability of the new approaches is tested using measurement data obtained during the Physics of Stratocumulus Top (POST airborne research campaign as well as synthetic turbulence data. They appear useful and complementary to existing methods. We show the number-of-crossings-based approaches respond differently to errors due to finite sampling and finite averaging than the classical power spectral method. Hence, their application for the case of short signals and small sampling frequencies is particularly interesting, as it can increase the robustness of turbulent kinetic energy dissipation rate retrieval.

  9. Enzymatic Kinetic Resolution of 2-Piperidineethanol for the Enantioselective Targeted and Diversity Oriented Synthesis

    Directory of Open Access Journals (Sweden)

    Dario Perdicchia

    2015-12-01

    Full Text Available 2-Piperidineethanol (1 and its corresponding N-protected aldehyde (2 were used for the synthesis of several natural and synthetic compounds. The existence of a stereocenter at position 2 of the piperidine skeleton and the presence of an easily-functionalized group, such as the alcohol, set 1 as a valuable starting material for enantioselective synthesis. Herein, are presented both synthetic and enzymatic methods for the resolution of the racemic 1, as well as an overview of synthesized natural products starting from the enantiopure 1.

  10. Hydrolytic Stability of Boronate Ester-Linked Covalent Organic Frameworks

    KAUST Repository

    Li, Huifang; Li, Haoyuan; Dai, Qingqing; Li, Hong; Bredas, Jean-Luc

    2018-01-01

    by reducing the energy barrier by a factor of 3. Importantly, the hydrolysis of boronate ester bonds situated in a COF environment follows reaction pathways that are different and have increased energy barriers. These results point to an enhanced hydrolytic

  11. Marine Microorganisms as Source of Stereoselective Esterases and Ketoreductases: Kinetic Resolution of a Prostaglandin Intermediate

    KAUST Repository

    De Vitis, Valerio; Guidi, Benedetta; Contente, Martina Letizia; Granato, Tiziana Mariarita; Conti, Paola; Molinari, Francesco; Crotti, Elena; Mapelli, Francesca; Borin, Sara S.; Daffonchio, Daniele; Romano, Diego

    2014-01-01

    A screening among bacterial strains isolated from water-brine interface of the deep hypersaline anoxic basins (DHABs) of the Eastern Mediterranean was carried out for the biocatalytical resolution of racemic propyl ester of anti-2-oxotricyclo[2.2.1.0]heptan-7-carboxylic acid (R,S)-1, a key intermediate for the synthesis of d-cloprostenol. Bacillus horneckiae 15A gave highly stereoselective reduction of (R,S)-1, whereas Halomonas aquamarina 9B enantioselectively hydrolysed (R,S)-1; in both cases, enantiomerically pure unreacted (R)-1 could be easily recovered and purified at molar conversion below 57–58 %, showing the potential of DHAB extremophile microbiome and marine-derived enzymes in stereoselective biocatalysis.

  12. Marine Microorganisms as Source of Stereoselective Esterases and Ketoreductases: Kinetic Resolution of a Prostaglandin Intermediate

    KAUST Repository

    De Vitis, Valerio

    2014-09-30

    A screening among bacterial strains isolated from water-brine interface of the deep hypersaline anoxic basins (DHABs) of the Eastern Mediterranean was carried out for the biocatalytical resolution of racemic propyl ester of anti-2-oxotricyclo[2.2.1.0]heptan-7-carboxylic acid (R,S)-1, a key intermediate for the synthesis of d-cloprostenol. Bacillus horneckiae 15A gave highly stereoselective reduction of (R,S)-1, whereas Halomonas aquamarina 9B enantioselectively hydrolysed (R,S)-1; in both cases, enantiomerically pure unreacted (R)-1 could be easily recovered and purified at molar conversion below 57–58 %, showing the potential of DHAB extremophile microbiome and marine-derived enzymes in stereoselective biocatalysis.

  13. Effects of Resolution on the Simulation of Boundary-layer Clouds and the Partition of Kinetic Energy to Subgrid Scales

    Directory of Open Access Journals (Sweden)

    Anning Cheng

    2010-02-01

    Full Text Available Seven boundary-layer cloud cases are simulated with UCLA-LES (The University of California, Los Angeles – large eddy simulation model with different horizontal and vertical gridspacing to investigate how the results depend on gridspacing. Some variables are more sensitive to horizontal gridspacing, while others are more sensitive to vertical gridspacing, and still others are sensitive to both horizontal and vertical gridspacings with similar or opposite trends. For cloud-related variables having the opposite dependence on horizontal and vertical gridspacings, changing the gridspacing proportionally in both directions gives the appearance of convergence. In this study, we mainly discuss the impact of subgrid-scale (SGS kinetic energy (KE on the simulations with coarsening of horizontal and vertical gridspacings. A running-mean operator is used to separate the KE of the high-resolution benchmark simulations into that of resolved scales of coarse-resolution simulations and that of SGSs. The diagnosed SGS KE is compared with that parameterized by the Smagorinsky-Lilly SGS scheme at various gridspacings. It is found that the parameterized SGS KE for the coarse-resolution simulations is usually underestimated but the resolved KE is unrealistically large, compared to benchmark simulations. However, the sum of resolved and SGS KEs is about the same for simulations with various gridspacings. The partitioning of SGS and resolved heat and moisture transports is consistent with that of SGS and resolved KE, which means that the parameterized transports are underestimated but resolved-scale transports are overestimated. On the whole, energy shifts to large-scales as the horizontal gridspacing becomes coarse, hence the size of clouds and the resolved circulation increase, the clouds become more stratiform-like with an increase in cloud fraction, cloud liquid-water path and surface precipitation; when coarse vertical gridspacing is used, cloud sizes do not

  14. Stereoselectivity and substrate specificity in the kinetic resolution of methyl-substituted 1-oxaspiro[2.5]octanes by Rhodotorula glutinis epoxide hydrolase

    NARCIS (Netherlands)

    Weijers, C.A.G.M.; Meeuwse, P.; Herpers, R.L.J.M.; Franssen, M.C.R.; Sudhölter, E.J.R.

    2005-01-01

    [GRAPHICS] The kinetic resolution of a range of methyl-substituted 1-oxaspiro[2.5]octanes by yeast epoxide hydrolase (YEH) from Rhodotorula glutinis has been investigated. The structural determinants of substrate specificity and stereoselectivity of YEH toward these substrates appeared to be the

  15. Chemo-enzymatic Baeyer-Villiger oxidation of 4-methylcyclohexanone via kinetic resolution of racemic carboxylic acids: direct access to enantioenriched lactone.

    Science.gov (United States)

    Drożdż, Agnieszka; Chrobok, Anna

    2016-01-21

    A new method for the asymmetric chemo-enzymatic Baeyer-Villiger oxidation of prochiral 4-methylcyclohexanone to (R)-4-methylcaprolactone in the presence of (±)-4-methyloctanoic acid, Candida Antarctica lipase B and 30% aq. H2O2 has been developed. A mechanism for the asymmetric induction based on kinetic resolution of racemic carboxylic acids is proposed.

  16. Kinetic energy measurement of hydrogen in LHD peripheral plasma with a multi-wavelength-range fine-resolution spectrometer

    International Nuclear Information System (INIS)

    Fujii, Keisuke; Mizushiri, Keisuke; Nishioka, Tomomi; Shikama, Taiichi; Iwamae, Atsushi; Goto, Motoshi; Morita, Shigeru; Hasuo, Masahiro

    2010-01-01

    We have simultaneously measured high resolution emission spectra of the hydrogen atomic Balmer-α, -β, -γ lines and molecular Fulcher-α band for a LHD peripheral plasma generated under a central magnetic field strength of 0.4 T. It is found that the velocity distributions of excited atoms calculated from the Balmer-α, -β, and -γ line shapes show similar profiles to each other. The translational kinetic energy corresponding to the average velocity is about 13 eV, which is about 300 times larger than the rotational energy of hydrogen molecules estimated from the line intensities in the Fulcher-α band. The velocity distributions differ from Maxwellian and have a high velocity tail over 1x10 5 m/s. A correlation between the high velocity tail and the electron temperature and density is seen and suggesting the excited atoms having such high velocities to be generated by the charge exchange collisions from high velocity protons in the peripheral region.

  17. The hydrolytic stage in high solids temperature phased anaerobic digestion improves the downstream methane production rate.

    Science.gov (United States)

    Buffière, P; Dooms, M; Hattou, S; Benbelkacem, H

    2018-07-01

    The role of the hydrolytic stage in high solids temperature phased anaerobic digestion was investigated with a mixture of cattle slurry and maize silage with variable ratios (100, 70 and 30% volatile solids coming from cattle slurry). It was incubated for 48 h at 37, 55, 65 and 72 °C. Soluble chemical oxygen demand and biochemical methane potential were measured at 0, 24 and 48 h. Higher temperatures improved the amount of solubilized COD, which confirmed previously reported results. Nevertheless, solubilization mostly took place during the first 24 h. The rate of methane production in post-hydrolysis BMPs increased after 48 h hydrolysis time, but not after 24 h. The first order kinetic constant rose by 40% on average. No correlation was observed between soluble COD and downstream methane production rate, indicating a possible modification of the physical structure of the particulate solids during the hydrolytic stage. Copyright © 2018 Elsevier Ltd. All rights reserved.

  18. New approaches for the reliable in vitro assessment of binding affinity based on high-resolution real-time data acquisition of radioligand-receptor binding kinetics.

    Science.gov (United States)

    Zeilinger, Markus; Pichler, Florian; Nics, Lukas; Wadsak, Wolfgang; Spreitzer, Helmut; Hacker, Marcus; Mitterhauser, Markus

    2017-12-01

    Resolving the kinetic mechanisms of biomolecular interactions have become increasingly important in early-phase drug development. Since traditional in vitro methods belong to dose-dependent assessments, binding kinetics is usually overlooked. The present study aimed at the establishment of two novel experimental approaches for the assessment of binding affinity of both, radiolabelled and non-labelled compounds targeting the A 3 R, based on high-resolution real-time data acquisition of radioligand-receptor binding kinetics. A novel time-resolved competition assay was developed and applied to determine the K i of eight different A 3 R antagonists, using CHO-K1 cells stably expressing the hA 3 R. In addition, a new kinetic real-time cell-binding approach was established to quantify the rate constants k on and k off , as well as the dedicated K d of the A 3 R agonist [ 125 I]-AB-MECA. Furthermore, lipophilicity measurements were conducted to control influences due to physicochemical properties of the used compounds. Two novel real-time cell-binding approaches were successfully developed and established. Both experimental procedures were found to visualize the kinetic binding characteristics with high spatial and temporal resolution, resulting in reliable affinity values, which are in good agreement with values previously reported with traditional methods. Taking into account the lipophilicity of the A 3 R antagonists, no influences on the experimental performance and the resulting affinity were investigated. Both kinetic binding approaches comprise tracer administration and subsequent binding to living cells, expressing the dedicated target protein. Therefore, the experiments resemble better the true in vivo physiological conditions and provide important markers of cellular feedback and biological response.

  19. Enantioselective Synthesis of Aminodiols by Sequential Rhodium-Catalysed Oxyamination/Kinetic Resolution: Expanding the Substrate Scope of Amidine-Based Catalysis.

    Science.gov (United States)

    Guasch, Joan; Giménez-Nueno, Irene; Funes-Ardoiz, Ignacio; Bernús, Miguel; Matheu, M Isabel; Maseras, Feliu; Castillón, Sergio; Díaz, Yolanda

    2018-03-26

    Regio- and stereoselective oxyamination of dienes through a tandem rhodium-catalysed aziridination-nucleophilic opening affords racemic oxazolidinone derivatives, which undergo a kinetic resolution acylation process with amidine-based catalysts (ABCs) to achieve s values of up to 117. This protocol was applied to the enantioselective synthesis of sphingosine. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. A study of pH-dependent photodegradation of amiloride by a multivariate curve resolution approach to combined kinetic and acid-base titration UV data.

    Science.gov (United States)

    De Luca, Michele; Ioele, Giuseppina; Mas, Sílvia; Tauler, Romà; Ragno, Gaetano

    2012-11-21

    Amiloride photostability at different pH values was studied in depth by applying Multivariate Curve Resolution Alternating Least Squares (MCR-ALS) to the UV spectrophotometric data from drug solutions exposed to stressing irradiation. Resolution of all degradation photoproducts was possible by simultaneous spectrophotometric analysis of kinetic photodegradation and acid-base titration experiments. Amiloride photodegradation showed to be strongly dependent on pH. Two hard modelling constraints were sequentially used in MCR-ALS for the unambiguous resolution of all the species involved in the photodegradation process. An amiloride acid-base system was defined by using the equilibrium constraint, and the photodegradation pathway was modelled taking into account the kinetic constraint. The simultaneous analysis of photodegradation and titration experiments revealed the presence of eight different species, which were differently distributed according to pH and time. Concentration profiles of all the species as well as their pure spectra were resolved and kinetic rate constants were estimated. The values of rate constants changed with pH and under alkaline conditions the degradation pathway and photoproducts also changed. These results were compared to those obtained by LC-MS analysis from drug photodegradation experiments. MS analysis allowed the identification of up to five species and showed the simultaneous presence of more than one acid-base equilibrium.

  1. Hydrolytic gain during hydrolysis reactions : implications and correction procedures

    NARCIS (Netherlands)

    Marchal, L.M.; Tramper, J.

    1999-01-01

    Some of the structural parameters of starch (e.g. % beta- or gluco-hydrolysis) were influenced by the increase in mass during the hydrolysis reactions (hydrolytic gain). Procedures were derived to correct this apparent % of hydrolysis to actual % of hydrolysis. These analytically derived equations

  2. Compressive strength and hydrolytic stability of fly ash based geopolymers

    Directory of Open Access Journals (Sweden)

    Nikolić Irena

    2013-01-01

    Full Text Available The process of geopolymerization involves the reaction of solid aluminosilicate materials with highly alkaline silicate solution yielding an aluminosilicate inorganic polymer named geopolymer, which may be successfully applied in civil engineering as a replacement for cement. In this paper we have investigated the influence of synthesis parameters: solid to liquid ratio, NaOH concentration and the ratio of Na2SiO3/NaOH, on the mechanical properties and hydrolytic stability of fly ash based geopolymers in distilled water, sea water and simulated acid rain. The highest value of compressive strength was obtained using 10 mol dm-3 NaOH and at the Na2SiO3/NaOH ratio of 1.5. Moreover, the results have shown that mechanical properties of fly ash based geopolymers are in correlation with their hydrolytic stability. Factors that increase the compressive strength also increase the hydrolytic stability of fly ash based geopolymers. The best hydrolytic stability of fly ash based geopolymers was shown in sea water while the lowest stability was recorded in simulated acid rain. [Projekat Ministarstva nauke Republike Srbije, br. 172054 i Nanotechnology and Functional Materials Center, funded by the European FP7 project No. 245916

  3. Molecular Imaging of Hydrolytic Enzymes Using PET and SPECT

    OpenAIRE

    Rempel, Brian P.; Price, Eric W.; Phenix, Christopher P.

    2017-01-01

    Hydrolytic enzymes are a large class of biological catalysts that play a vital role in a plethora of critical biochemical processes required to maintain human health. However, the expression and/or activity of these important enzymes can change in many different diseases and therefore represent exciting targets for the development of positron emission tomography (PET) and single-photon emission computed tomography (SPECT) radiotracers. This review focuses on recently reported radiolabeled sub...

  4. A method to measure hydrolytic activity of adenosinetriphosphatases (ATPases.

    Directory of Open Access Journals (Sweden)

    Gianluca Bartolommei

    Full Text Available The detection of small amounts (nanomoles of inorganic phosphate has a great interest in biochemistry. In particular, phosphate detection is useful to evaluate the rate of hydrolysis of phosphatases, that are enzymes able to remove phosphate from their substrate by hydrolytic cleavage. The hydrolysis rate is correlated to enzyme activity, an extremely important functional parameter. Among phosphatases there are the cation transporting adenosinetriphosphatases (ATPases, that produce inorganic phosphate by cleavage of the γ-phosphate of ATP. These membrane transporters have many fundamental physiological roles and are emerging as potential drug targets. ATPase hydrolytic activity is measured to test enzyme functionality, but it also provides useful information on possible inhibitory effects of molecules that interfere with the hydrolytic process. We have optimized a molybdenum-based protocol that makes use of potassium antimony (III oxide tartrate (originally employed for phosphate detection in environmental analysis to allow its use with phosphatase enzymes. In particular, the method was successfully applied to native and recombinant ATPases to demonstrate its reliability, validity, sensitivity and versatility. Our method introduces significant improvements to well-established experimental assays, which are currently employed for ATPase activity measurements. Therefore, it may be valuable in biochemical and biomedical investigations of ATPase enzymes, in combination with more specific tests, as well as in high throughput drug screening.

  5. Influence of the partial volume correction method on (18)F-fluorodeoxyglucose brain kinetic modelling from dynamic PET images reconstructed with resolution model based OSEM.

    Science.gov (United States)

    Bowen, Spencer L; Byars, Larry G; Michel, Christian J; Chonde, Daniel B; Catana, Ciprian

    2013-10-21

    Kinetic parameters estimated from dynamic (18)F-fluorodeoxyglucose ((18)F-FDG) PET acquisitions have been used frequently to assess brain function in humans. Neglecting partial volume correction (PVC) for a dynamic series has been shown to produce significant bias in model estimates. Accurate PVC requires a space-variant model describing the reconstructed image spatial point spread function (PSF) that accounts for resolution limitations, including non-uniformities across the field of view due to the parallax effect. For ordered subsets expectation maximization (OSEM), image resolution convergence is local and influenced significantly by the number of iterations, the count density, and background-to-target ratio. As both count density and background-to-target values for a brain structure can change during a dynamic scan, the local image resolution may also concurrently vary. When PVC is applied post-reconstruction the kinetic parameter estimates may be biased when neglecting the frame-dependent resolution. We explored the influence of the PVC method and implementation on kinetic parameters estimated by fitting (18)F-FDG dynamic data acquired on a dedicated brain PET scanner and reconstructed with and without PSF modelling in the OSEM algorithm. The performance of several PVC algorithms was quantified with a phantom experiment, an anthropomorphic Monte Carlo simulation, and a patient scan. Using the last frame reconstructed image only for regional spread function (RSF) generation, as opposed to computing RSFs for each frame independently, and applying perturbation geometric transfer matrix PVC with PSF based OSEM produced the lowest magnitude bias kinetic parameter estimates in most instances, although at the cost of increased noise compared to the PVC methods utilizing conventional OSEM. Use of the last frame RSFs for PVC with no PSF modelling in the OSEM algorithm produced the lowest bias in cerebral metabolic rate of glucose estimates, although by less than 5% in

  6. An improved experimental scheme for simultaneous measurement of high-resolution zero electron kinetic energy (ZEKE) photoelectron and threshold photoion (MATI) spectra

    Science.gov (United States)

    Michels, François; Mazzoni, Federico; Becucci, Maurizio; Müller-Dethlefs, Klaus

    2017-10-01

    An improved detection scheme is presented for threshold ionization spectroscopy with simultaneous recording of the Zero Electron Kinetic Energy (ZEKE) and Mass Analysed Threshold Ionisation (MATI) signals. The objective is to obtain accurate dissociation energies for larger molecular clusters by simultaneously detecting the fragment and parent ion MATI signals with identical transmission. The scheme preserves an optimal ZEKE spectral resolution together with excellent separation of the spontaneous ion and MATI signals in the time-of-flight mass spectrum. The resulting improvement in sensitivity will allow for the determination of dissociation energies in clusters with substantial mass difference between parent and daughter ions.

  7. Multivariate curve resolution applied to kinetic-spectroscopic data matrices: Dye determination in foods by means of enzymatic oxidation.

    Science.gov (United States)

    Boeris, Valeria; Arancibia, Juan A; Olivieri, Alejandro C

    2017-07-01

    In this work, the combination of chemometric techniques with kinetic-spectroscopic data allowed quantifying two dyes (tartrazine and carminic acid) in complex matrices as mustard, ketchup, asparagus soup powder, pumpkin soup powder, plum jam and orange-strawberry juice. Quantitative analysis was performed without the use of tedious sample pretreatment, due to the achievement of the second-order advantage. The results obtained showed an improvement in simplicity, speed and cost with respect to usual separation techniques, allowing to properly quantifying these dyes obtaining limits of detection below 0.6mgL -1 . In addition, to the best of our knowledge, is the first time that kinetic-spectroscopic data are obtained from the action of laccase for analytical purposes. Copyright © 2017 Elsevier B.V. All rights reserved.

  8. Evaluation of wild herbivore faeces from South Africa as a potential source of hydrolytically active microorganisms

    CSIR Research Space (South Africa)

    Ndlela, LL

    2016-02-01

    Full Text Available once hydrolysis (FDA) or reduction (TTC) occurred. The fluorescein diacetate assay operates on the princi- ple of hydrolytic release of two acetate groups via ester bond cleavage by free and membrane-bound hydrolytic enzymes, yielding the yellow... hydrolytic enzymes such as amylases can cleave its ester bonds as well (Lundgren 1981; Green et  al. 2006). The FDA hydrolysis assay has also been utilised and recommended as an efficient method to estimate active cells within environmental samples...

  9. Hydrolytic Stability of Boronate Ester-Linked Covalent Organic Frameworks

    KAUST Repository

    Li, Huifang

    2018-01-30

    The stability of covalent organic frameworks (COFs) is essential to their applications. However, the common boronate ester-linked COFs are susceptible to attack by nucleophiles (such as water molecules) at the electron-deficient boron sites. To provide an understanding of the hydrolytic stability of the representative boronate ester-linked COF-5 and of the associated hydrolysis mechanisms, density functional theory (DFT) calculations were performed to characterize the hydrolysis reactions of the molecule formed by the condensation of 1,4-phenylenebis(boronic acid) (PBBA) and 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) monomers; two cases were considered, one dealing with the freestanding molecule and the other with the molecule interacting with COF layers. It was found that the boronate ester (B–O) bond dissociation, which requires one H2O molecule, has a relatively high energy barrier of 22.3 kcal mol−1. However, the presence of an additional H2O molecule significantly accelerates hydrolysis by reducing the energy barrier by a factor of 3. Importantly, the hydrolysis of boronate ester bonds situated in a COF environment follows reaction pathways that are different and have increased energy barriers. These results point to an enhanced hydrolytic stability of COF-5 crystals.

  10. Thermal and Hydrolytic Stability of Dithiophophoric Acids Stabilité thermique et hydrolytique des acides dithiophosphoriques

    Directory of Open Access Journals (Sweden)

    Ivanov S. K.

    2006-11-01

    Full Text Available The thermal and hydrolytic stability of dibutyl-, diisobutyl- and diisooctyldithiophosphoric acids have been studied in the range of 40-80°C. The reaction progress was followed by the H2S evolution kinetics in volumetric equipment at constant pressure, equal to the barometric one. The kinetic parameters of the process have been determined at various acid water ratios - maximum rates of gas evolution, activation energy and the kinetic order. It has been shown that the hydrolysis proceeds mainly along the sulph-hydrate group of the acid (up to temperatures of 60°C, while at higher temperatures the ester groups and the thion sulphur are attacked too. The thermal stability of dithiophosphoric acids has been studied in the presence of stainless steel, lead and copper plates. It has been shown that stainless steel doesn't affect the process rate, while copper and especially lead increase the gas evolution and decrease the activation energy. A model describing the reaction progress at the interfacial surfaces - organic phase, water and metal surface - has been developed. Based on these data a conclusion is advanced, related to the manifacture technology of antioxidant, anticorrosion and antiwear additives of the zinc dialkyldithiophosphate type. It is pointed out that the neutralization process of dithiophosphoric acids should be carried out in a stainless steel reactor at tempeatures below 70°C. Le présent article s'efforce d'élucider l'influence de l'eau, de la température et des surfaces métalliques sur la stabilité thermique et hydrolytique des acides dibutyl-, diisobutyl- et diisooctyldithiophosphoriques, à la lumière du concept d'interaction.

  11. Access to Optically Pure β-Hydroxy Esters via Non-Enzymatic Kinetic Resolution by a Planar-Chiral DMAP Catalyst

    Directory of Open Access Journals (Sweden)

    Alba E. Díazlvarez

    2014-09-01

    Full Text Available The development of new approaches to obtain optically pure β-hydroxy esters is an important area in synthetic organic chemistry since they are precursors of other high value compounds. Herein, the kinetic resolution of racemic β-hydroxy esters using a planar-chiral DMAP derivative catalyst is presented. Following this procedure, a range of aromatic β-hydroxy esters was obtained in excellent selectivities (up to s = 107 and high enantiomeric excess (up to 99% ee. Furthermore, the utility of the present method was demonstrated in the synthesis of (S-3-hydroxy-N-methyl-3-phenylpropanamide, a key intermediate for bioactive molecules such as fluoxetine, tomoxetine or nisoxetine, in its enantiomerically pure form.

  12. omega-Amino acid:pyruvate transaminase from Alcaligenes denitrificans Y2k-2: a new catalyst for kinetic resolution of beta-amino acids and amines.

    Science.gov (United States)

    Yun, Hyungdon; Lim, Seongyop; Cho, Byung-Kwan; Kim, Byung-Gee

    2004-04-01

    Alcaligenes denitrificans Y2k-2 was obtained by selective enrichment followed by screening from soil samples, which showed omega-amino acid:pyruvate transaminase activity, to kinetically resolve aliphatic beta-amino acid, and the corresponding structural gene (aptA) was cloned. The gene was functionally expressed in Escherichia coli BL21 by using an isopropyl-beta-D-thiogalactopyranoside (IPTG)-inducible pET expression system (9.6 U/mg), and the recombinant AptA was purified to show a specific activity of 77.2 U/mg for L-beta-amino-n-butyric acid (L-beta-ABA). The enzyme converts various beta-amino acids and amines to the corresponding beta-keto acids and ketones by using pyruvate as an amine acceptor. The apparent K(m) and V(max) for L-beta-ABA were 56 mM and 500 U/mg, respectively, in the presence of 10 mM pyruvate. In the presence of 10 mM L-beta-ABA, the apparent K(m) and V(max) for pyruvate were 11 mM and 370 U/mg, respectively. The enzyme exhibits high stereoselectivity (E > 80) in the kinetic resolution of 50 mM D,L-beta-ABA, producing optically pure D-beta-ABA (99% enantiomeric excess) with 53% conversion.

  13. ω-Amino Acid:Pyruvate Transaminase from Alcaligenes denitrificans Y2k-2: a New Catalyst for Kinetic Resolution of β-Amino Acids and Amines

    Science.gov (United States)

    Yun, Hyungdon; Lim, Seongyop; Cho, Byung-Kwan; Kim, Byung-Gee

    2004-01-01

    Alcaligenes denitrificans Y2k-2 was obtained by selective enrichment followed by screening from soil samples, which showed ω-amino acid:pyruvate transaminase activity, to kinetically resolve aliphatic β-amino acid, and the corresponding structural gene (aptA) was cloned. The gene was functionally expressed in Escherichia coli BL21 by using an isopropyl-β-d-thiogalactopyranoside (IPTG)-inducible pET expression system (9.6 U/mg), and the recombinant AptA was purified to show a specific activity of 77.2 U/mg for l-β-amino-n-butyric acid (l-β-ABA). The enzyme converts various β-amino acids and amines to the corresponding β-keto acids and ketones by using pyruvate as an amine acceptor. The apparent Km and Vmax for l-β-ABA were 56 mM and 500 U/mg, respectively, in the presence of 10 mM pyruvate. In the presence of 10 mM l-β-ABA, the apparent Km and Vmax for pyruvate were 11 mM and 370 U/mg, respectively. The enzyme exhibits high stereoselectivity (E > 80) in the kinetic resolution of 50 mM d,l-β-ABA, producing optically pure d-β-ABA (99% enantiomeric excess) with 53% conversion. PMID:15066855

  14. In Vivo Optical Imaging for Targeted Drug Kinetics and Localization for Oral Surgery and Super-Resolution, Facilitated by Printed Phantoms

    Science.gov (United States)

    Bentz, Brian Z.

    Many human cancer cell types over-express folate receptors, and this provides an opportunity to develop targeted anti-cancer drugs. For these drugs to be effective, their kinetics must be well understood in vivo and in deep tissue where tumors occur. We demonstrate a method for imaging these parameters by incorporating a kinetic compartment model and fluorescence into optical diffusion tomography (ODT). The kinetics were imaged in a live mouse, and found to be in agreement with previous in vitro studies, demonstrating the validity of the method and its feasibility as an effective tool in preclinical drug development studies. Progress in developing optical imaging for biomedical applications requires customizable and often complex objects known as "phantoms" for testing and evaluation. We present new optical phantoms fabricated using inexpensive 3D printing methods with multiple materials, allowing for the placement of complex inhomogeneities in heterogeneous or anatomically realistic geometries, as opposed to previous phantoms which were limited to simple shapes formed by molds or machining. Furthermore, we show that Mie theory can be used to design the optical properties to match a target tissue. The phantom fabrication methods are versatile, can be applied to optical imaging methods besides diffusive imaging, and can be used in the calibration of live animal imaging data. Applications of diffuse optical imaging in the operating theater have been limited in part due to computational burden. We present an approach for the fast localization of arteries in the roof of the mouth that has the potential to reduce complications. Furthermore, we use the extracted position information to fabricate a custom surgical guide using 3D printing that could protect the arteries during surgery. The resolution of ODT is severely limited by the attenuation of high spatial frequencies. We present a super-resolution method achieved through the point localization of fluorescent

  15. High performance dental resin composites with hydrolytically stable monomers.

    Science.gov (United States)

    Wang, Xiaohong; Huyang, George; Palagummi, Sri Vikram; Liu, Xiaohui; Skrtic, Drago; Beauchamp, Carlos; Bowen, Rafael; Sun, Jirun

    2018-02-01

    The objectives of this project were to: 1) develop strong and durable dental resin composites by employing new monomers that are hydrolytically stable, and 2) demonstrate that resin composites based on these monomers perform superiorly to the traditional bisphenol A glycidyl dimethacrylate/triethylene glycol dimethacrylate (Bis-GMA/TEGDMA) composites under testing conditions relevant to clinical applications. New resins comprising hydrolytically stable, ether-based monomer, i.e., triethylene glycol divinylbenzyl ether (TEG-DVBE), and urethane dimethacrylate (UDMA) were produced via composition-controlled photo-polymerization. Their composites contained 67.5wt% of micro and 7.5wt% of nano-sized filler. The performances of both copolymers and composites were evaluated by a battery of clinically-relevant assessments: degree of vinyl conversion (DC: FTIR and NIR spectroscopy); refractive index (n: optical microscopy); elastic modulus (E), flexural strength (F) and fracture toughness (K IC ) (universal mechanical testing); Knoop hardness (HK; indentation); water sorption (W sp ) and solubility (W su ) (gravimetry); polymerization shrinkage (S v ; mercury dilatometry) and polymerization stress (tensometer). The experimental UDMA/TEG-DVBE composites were compared with the Bis-GMA/TEGDMA composites containing the identical filler contents, and with the commercial micro hybrid flowable composite. UDMA/TEG-DBVE composites exhibited n, E, W sp , W su and S v equivalent to the controls. They outperformed the controls with respect to F (up to 26.8% increase), K IC (up to 27.7% increase), modulus recovery upon water sorption (full recovery vs. 91.9% recovery), and stress formation (up to 52.7% reduction). In addition, new composites showed up to 27.7% increase in attainable DC compared to the traditional composites. Bis-GMA/TEGDMA controls exceeded the experimental composites with respect to only one property, the composite hardness. Significantly, up to 18.1% lower HK values in

  16. Nucleophilic addition to olefins. 5. Reaction of 1,1-dinitro-2,2-diphenylethylene with water and hydroxide ion in 50% Me2SO-50% water. Complete kinetic analysis of hydrolytic cleavage of the C=C double bond in acidic and basic solution

    International Nuclear Information System (INIS)

    Bernasconi, C.F.; Carre, D.J.; Kanavarioti, A.

    1981-01-01

    Hydrolysis of 1,1-dinitro-2,2-diphenylethylene (2) to form benzophenone and dinitromethane (or its anion) was studied in 50% Me 2 SO-50% H 2 O and also in 50% Me 2 SO-50% D 2 O at pHs of 1 to 16. Solvent isotope effects general acid and general base catalysis, and structure-reactivity relationships were used to study the kinetics. The conclusions are the following: (1) the equilibrium constants for OH - and water addition to 2 to form T/sub OH/ - are comparable to those for the corresponding reactions of benzylidene Meldrum's acid (1), but the rate constants are much lower for 2 than for 1; (2) carbon protonation of T/sub OH/ - follows an Eigen curve similar to that for 1,1-dinitroethane anion but which is displaced upward by nearly 1 log unit. This indicates a higher intrinsic protonation rate because of a smaller charge delocalization in T/sub OH/ - owing to an enhanced steric hindrance to coplanarity of the nitro groups in T/sub OH/ - ; (3) intramolecular proton transfer from the OH group to the carbanionic site in T/sub OH/ - is insignificant, which is in contrast to the behavior of the addition complex between 2 and morpholine; (4) the base-catalyzed breakdown of T/sub OH/ 0 into benzophenone and dinitromethane anion occurs by rate-limiting oxygen deprotonation, which implies that k 4 for CH(NO 2 ) 2 - departure from T/sub OH/ 0- is much greater than 2 x 10 9 s -1 , a remarkably high rate for a carbanionic leaving group. The water-catalyzed breakdown of T/sub OH/ 0 proceeds by a different mechanism, which is most likely concerted, with a transition state; (5) the acid-catalyzed breakdown of T/sub OH/ 2- occurs by rate-limiting carbon protonation (k 6 /sup BH/), but the water-catalyzed breakdown follows a different mechanism. Various possibilities are discussed, and a slight preference is given to a preassociation mechanism

  17. Technological advances and applications of hydrolytic enzymes for valorization of lignocellulosic biomass.

    Science.gov (United States)

    Manisha; Yadav, Sudesh Kumar

    2017-12-01

    Hydrolytic enzymes are indispensable tools in the production of various foodstuffs, drugs, and consumables owing to their applications in almost every industrial process nowadays. One of the foremost areas of interest involving the use of hydrolytic enzymes is in the transformation of lignocellulosic biomass into value added products. However, limitations of the processes due to inadequate enzyme activity and stability with a narrow range of pH and temperature optima often limit their effective usage. The innovative technologies, involving manipulation of enzyme activity and stability through mutagenesis, genetic engineering and metagenomics lead to a major leap in all the fields using hydrolytic enzymes. This article provides recent advancement towards the isolation and use of microbes for lignocellulosic biomass utilisation, microbes producing the hydrolytic enzymes, the modern age technologies used to manipulate and enhance the hydrolytic enzyme activity and the applications of such enzymes in value added products development from lignocellulosic biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Non-hydrolytic metal oxide films for perovskite halide overcoating and stabilization

    Science.gov (United States)

    Martinson, Alex B.; Kim, In Soo

    2017-09-26

    A method of protecting a perovskite halide film from moisture and temperature includes positioning the perovskite halide film in a chamber. The chamber is maintained at a temperature of less than 200 degrees Celsius. An organo-metal compound is inserted into the chamber. A non-hydrolytic oxygen source is subsequently inserted into the chamber. The inserting of the organo-metal compound and subsequent inserting of the non-hydrolytic oxygen source into the chamber is repeated for a predetermined number of cycles. The non-hydrolytic oxygen source and the organo-metal compound interact in the chamber to deposit a non-hydrolytic metal oxide film on perovskite halide film. The non-hydrolytic metal oxide film protects the perovskite halide film from relative humidity of greater than 35% and a temperature of greater than 150 degrees Celsius, respectively.

  19. PMMA/Ca2+ bone cements. Hydrolytic properties and bioactivity

    Directory of Open Access Journals (Sweden)

    Mónica L. Hernández

    2012-01-01

    Full Text Available Bone cements of poly (methyl methacrylate (PMMA have been used for about 40 years to fix artificial prosthesis to bone structure. The aim of this study was to evaluate the absorption, solubility, degradation and bioactivity of novel formulations of PMMA/Ca2+ bone cements. These properties were evaluated using a fractional experimental design. Hydrolytic parameters were determined, from which we found that 7/8 of the formulations for absorption and 6/8 for solubility fulfill the ISO 4049:2000 requirements. The final degradation values ranged between 1 and 5%, except for one of the formulations. Besides, some formulations showed bioactivity after seven days of immersion in SBF solution.

  20. Hydrolytic And Enzymatic Degradation Characteristics Of Biodegradable Aliphatic Polysters

    Institute of Scientific and Technical Information of China (English)

    LI Suming

    2004-01-01

    Aliphatic polyesters, especially those derived from lactide (PLA), glycolide (PGA) and ε-caprolactone (PCL), are being investigated worldwide for applications in the field of surgery (suture material, devices for internal bone fracture fixation), pharmacology (sustained drug delivery systems), and tissue engineering (scaffold for tissue regeneration) [1,2]. This is mainly due to their good biocompatibility and variable degradability. These polymers present also a growing interest for environmental applications in agriculture (mulch films) and in our everyday life (packaging material)as the development of biodegradable materials is now considered as one of the potential solutions to the problem of plastic waste management.For both biomedical and environmental applications, it is of major importance to understand the degradation characteristics of the polymers. The hydrolytic degradation of aliphatic polyesters has been investigated by many research groups. Our group has shown that degradation of PLAGA large size devices is faster inside than at the surface. This heterogeneous degradation is due to the autocatalytic effect of carboxylic endgroups formed by ester bond cleavage. Moreover,degradation-induced morphological and compositional changes were also elucidated. In the case of PCL, the hydrolytic degradation is very slow due to its hydrophobicity and crystallinity.The enzymatic degradation of these polymers has been investigated by a number of authors. A specific enzyme, proteinase K, has been shown to have significant effects on PLA degradation. This enzyme preferentially degrade L-lactate units as opposed to D-lactate ones, amorphous zones as opposed to crystalline ones [3]. The enzymatic degradation of PCL polymers has also been investigated. A number of lipase-type enzymes were found to significantly accelerate the degradation of PCL despite its high crystallinity. In the case of PLA/PCL blends, the two components exhibited well separated crystalline domains

  1. Cation dependency of the hydrolytic activity of activated bovine Protein C

    International Nuclear Information System (INIS)

    Hill, K.A.W.

    1986-01-01

    The hydrolytic activity of activated bovine plasma Protein C (APC) is dependent upon monovalent or divalent cations. The kinetics of APC activity were examined with a variety of monovalent and divalent cations, and significant differences were observed. Similar studies were performed with des(1-41, light chain)APC (GDAPC), from which all γ-carboxyglutamic acid residues have been removed. These studies provided useful information concerning the cation dependency. Divalent cations apparently stimulate APC and GDAPC kinetic activity through association at a single γ-carboxyglutamic acid-independent high affinity binding site. A Mn(II) binding site of this nature of GDAPC was determined by EPR spectroscopy, to possess a dissociation constant of 53 +/- 8 uM. Monovalent cations stimulate GDAPC activity through association at an apparently single binding site that is distinct from the divalent cation site. The monovalent cation , Tl(I), was determined, by 205 Tl(I) NMR spectroscopy, to bind to APC and GDAPC with dissociation constants of 16 +/- 8 mM and 32+/- 11 mM, respectively. Both NMR and EPR spectroscopy have been utilized to estimate topographical relationships between divalent cation sites, monovalent cation sites, and the active site of GDAPC. By observing the paramagnetic effects of either Mn(II) or an active site directed spin-label on the longitudinal relaxation rates of Tl(I) nuclei bound to this enzyme, the average interatomic distance between Mn(II) and Tl(I) was calculated to be 8.3 +/- 0.3 A, and the average distance between Tl(I) and the spin-label free electron was estimated to be 3.8 +/- 0.2 A

  2. Candida Rugosa Lipase-catalyzed Kinetic Resolution of 3-(Isobutyryloxy)methyl 4-[2-(Difluoromethoxy)phenyl]-2-methyl-5,5-dioxo-1,4-dihydrobenzothieno[3,2-b]pyridine-3-carboxylate

    NARCIS (Netherlands)

    Sobolev, A.; Zhalubovskis, R.; Franssen, M.C.R.; Vigante, B.; Chekavichus, B.; Duburs, G.; Groot, de Æ.

    2004-01-01

    The lipase-catalyzed kinetic resolution of 3-(isobutyryloxy)methyl 4-[2-(difluoromethoxy)phenyl]-2-methyl-5,5-dioxo-1,4-dihydrobenzothieno[3,2-b]pyridine-3-carboxylate has been performed. The most enantioselective reaction (E = 28) was transesterification with n-butanol in water-saturated toluene at

  3. High-Resolution Denitrification Kinetics in Pasture Soils Link N2O Emissions to pH, and Denitrification to C Mineralization.

    Directory of Open Access Journals (Sweden)

    Md Sainur Samad

    Full Text Available Denitrification in pasture soils is mediated by microbial and physicochemical processes leading to nitrogen loss through the emission of N2O and N2. It is known that N2O reduction to N2 is impaired by low soil pH yet controversy remains as inconsistent use of soil pH measurement methods by researchers, and differences in analytical methods between studies, undermine direct comparison of results. In addition, the link between denitrification and N2O emissions in response to carbon (C mineralization and pH in different pasture soils is still not well described. We hypothesized that potential denitrification rate and aerobic respiration rate would be positively associated with soils. This relationship was predicted to be more robust when a high resolution analysis is performed as opposed to a single time point comparison. We tested this by characterizing 13 different temperate pasture soils from northern and southern hemispheres sites (Ireland and New Zealand using a fully automated-high-resolution GC detection system that allowed us to detect a wide range of gas emissions simultaneously. We also compared the impact of using different extractants for determining pH on our conclusions. In all pH measurements, soil pH was strongly and negatively associated with both N2O production index (IN2O and N2O/(N2O+N2 product ratio. Furthermore, emission kinetics across all soils revealed that the denitrification rates under anoxic conditions (NO+N2O+N2 μmol N/h/vial were significantly associated with C mineralization (CO2 μmol/h/vial measured both under oxic (r2 = 0.62, p = 0.0015 and anoxic (r2 = 0.89, p<0.0001 conditions.

  4. Reorganization of lipid nanocapsules at air-water interface 3. Action of hydrolytic enzymes HLL and pancreatic PLA2.

    Science.gov (United States)

    Minkov, I; Ivanova, Tz; Panaiotov, I; Proust, J; Verger, R

    2005-09-25

    The action of the hydrolytic enzymes humicola lanuginosa lipase (HLL) and pancreatic phospholipase A2 (PLA2) on monolayers formed from lipid nanocapsules (LNC) and model monolayers containing their components, Labrafac, Solutol and Lipoid, is studied by simultaneous measuring the changes in the film area and the surface potential in the "zero order" trough at constant surface pressure (pi). The kinetic models describing the hydrolysis by HLL of the Labrafac, Solutol and their mixtures have been proposed. By using the developed theoretical approach together with the experimental results the surface concentrations of the substrates, hydrolysis products and values of the global kinetic constants were obtained. The comparison between the global kinetic constants in the case of HLL hydrolysis of pure Labrafac, Solutol monolayers and those of the model mixed Labrafac/Solutol monolayers, shows that the rates of hydrolysis are of the same order of magnitude, i.e. an additively of the HLL enzyme action is observed. The composition of the mixed Labrafac/Solutol monolayer, formed after the interfacial LNC destabilization, was estimated.

  5. Efficient Synthesis of Differentiated syn-1,2-Diol Derivatives by Asymmetric Transfer Hydrogenation-Dynamic Kinetic Resolution of α-Alkoxy-Substituted β-Ketoesters.

    Science.gov (United States)

    Monnereau, Laure; Cartigny, Damien; Scalone, Michelangelo; Ayad, Tahar; Ratovelomanana-Vidal, Virginie

    2015-08-10

    Asymmetric transfer hydrogenation was applied to a wide range of racemic aryl α-alkoxy-β-ketoesters in the presence of well-defined, commercially available, chiral catalyst Ru(II) -(N-p-toluenesulfonyl-1,2-diphenylethylenediamine) and a 5:2 mixture of formic acid and triethylamine as the hydrogen source. Under these conditions, dynamic kinetic resolution was efficiently promoted to provide the corresponding syn α-alkoxy-β-hydroxyesters derived from substituted aromatic and heteroaromatic aldehydes with a high level of diastereoselectivity (diastereomeric ratio (d.r.)>99:1) and an almost perfect enantioselectivity (enantiomeric excess (ee)>99 %). Additionally, after extensive screening of the reaction conditions, the use of Ru(II) - and Rh(III) -tethered precatalysts extended this process to more-challenging substrates that bore alkenyl-, alkynyl-, and alkyl substituents to provide the corresponding syn α-alkoxy-β-hydroxyesters with excellent enantiocontrol (up to 99 % ee) and good to perfect diastereocontrol (d.r.>99:1). Lastly, the synthetic utility of the present protocol was demonstrated by application to the asymmetric synthesis of chiral ester ethyl (2S)-2-ethoxy-3-(4-hydroxyphenyl)-propanoate, which is an important pharmacophore in a number of peroxisome proliferator-activated receptor α/γ dual agonist advanced drug candidates used for the treatment of type-II diabetes. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. General problems arising from the analogical resolution of the kinetic equations of nuclear reactors (1961); Problemes generaux poses par la resolution analogique des equations cinetiques des reacteurs nucleaires (1961)

    Energy Technology Data Exchange (ETDEWEB)

    Caillet, C [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1961-07-01

    The author reviews precisely the analogical techniques used for the resolution of the kinetic equations of nuclear reactors. Prior to this, he recalls the reasons which oblige physicians and engineers, even today, to use electronic machines in this domain. The author then considers the technological problems posed by the range of values which the various nuclear parameters adopt. In each case, he shows that a compromise is possible allowing an optimum precision. He compares the results to those obtained by arithmetic calculation and uses the examples chosen in a critical analysis of the present possibilities of the two methods of calculation. (author) [French] L'auteur cherche a faire un point aussi exact que possible des techniques analogiques utilisees pour resoudre les equations cinetiques des reacteurs nucleaires. Il rappelle auparavant les raisons pour lesquelles physiciens et ingenieurs sont obliges, encore aujourd'hui, de faire appel aux machines electroniques dans ce domaine. Puis il etudie les problemes technologiques que souleve le champ des valeurs prises par les differents parametres nucleaires. Dans chacun des cas, il montre l'existence d'un compromis qui permet d'atteindre une precision optimum. Il compare les resultats obtenus a ceux provenant de calculateurs arithmetiques et profite des exemples choisis pour faire une analyse critique des possibilites actuelles offertes par les deux modes de calcul. (auteur)

  7. Hydrolytically degradable polymer micelles for drug delivery: a SAXS/SANS kinetic study

    Czech Academy of Sciences Publication Activity Database

    Filippov, Sergey K.; Franklin, J. M.; Konarev, P. V.; Chytil, Petr; Etrych, Tomáš; Bogomolova, Anna; Dyakonova, M.; Papadakis, C. M.; Radulescu, A.; Ulbrich, Karel; Štěpánek, Petr; Svergun, D. I.

    2013-01-01

    Roč. 14, č. 11 (2013), s. 4061-4070 ISSN 1525-7797 R&D Projects: GA ČR GAP208/10/1600 Institutional support: RVO:61389013 Keywords : HPMA * micelles * drug release Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.788, year: 2013

  8. Hydrolytic bacteria in mesophilic and thermophilic degradation of plant biomass

    Energy Technology Data Exchange (ETDEWEB)

    Zverlov, Vladimir V.; Hiegl, Wolfgang; Koeck, Daniela E.; Koellmeier, Tanja; Schwarz, Wolfgang H. [Department of Microbiology, Technische Universitaet Muenchen, Freising-Weihenstephan (Germany); Kellermann, Josef [Max Planck Institute for Biochemistry, Am Klopferspitz, Martinsried (Germany)

    2010-12-15

    Adding plant biomass to a biogas reactor, hydrolysis is the first reaction step in the chain of biological events towards methane production. Maize silage was used to enrich efficient hydrolytic bacterial consortia from natural environments under conditions imitating those in a biogas plant. At 55-60 C a more efficient hydrolyzing culture could be isolated than at 37 C. The composition of the optimal thermophilic bacterial consortium was revealed by sequencing clones from a 16S rRNA gene library. A modified PCR-RFLP pre-screening method was used to group the clones. Pure anaerobic cultures were isolated. 70% of the isolates were related to Clostridium thermocellum. A new culture-independent method for identification of cellulolytic enzymes was developed using the isolation of cellulose-binding proteins. MALDI-TOF/TOF analysis and end-sequencing of peptides from prominent protein bands revealed cellulases from the cellulosome of C. thermocellum and from a major cellulase of Clostridium stercorarium. A combined culture of C. thermocellum and C. stercorarium was shown to excellently degrade maize silage. A spore preparation method suitable for inoculation of maize silage and optimal hydrolysis was developed for the thermophilic bacterial consortium. This method allows for concentration and long-term storage of the mixed culture for instance for inoculation of biogas fermenters. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  9. Lipase-catalyzed asymmetric synthesis of naphtho[2,3-c]furan-1(3H)-one derivatives by a one-pot dynamic kinetic resolution/intramolecular Diels-Alder reaction: Total synthesis of (-)-himbacine.

    Science.gov (United States)

    Sugiyama, Koji; Kawanishi, Shinji; Oki, Yasuhiro; Kamiya, Marin; Hanada, Ryosuke; Egi, Masahiro; Akai, Shuji

    2018-04-01

    One-pot sequential reactions using the acyl moieties installed by enzymatic dynamic kinetic resolution of alcohols have been little investigated. In this work, the acryloyl moiety installed via the lipase/oxovanadium combo-catalyzed dynamic kinetic resolution of a racemic dienol [4-(cyclohex-1-en-1-yl)but-3-en-2-ol or 1-(cyclohex-1-en-1-yl)but-2-en-1-ol] with a (Z)-3-(phenylsulfonyl)acrylate underwent an intramolecular Diels-Alder reaction in a one-pot procedure to produce an optically active naphtho[2,3-c]furan-1(3H)-one derivative (98% ee). This method was successfully applied to the asymmetric total synthesis of (-)-himbacine. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. Halophilic Bacteria as a Source of Novel Hydrolytic Enzymes

    Science.gov (United States)

    de Lourdes Moreno, María; Pérez, Dolores; García, María Teresa; Mellado, Encarnación

    2013-01-01

    Hydrolases constitute a class of enzymes widely distributed in nature from bacteria to higher eukaryotes. The halotolerance of many enzymes derived from halophilic bacteria can be exploited wherever enzymatic transformations are required to function under physical and chemical conditions, such as in the presence of organic solvents and extremes in temperature and salt content. In recent years, different screening programs have been performed in saline habitats in order to isolate and characterize novel enzymatic activities with different properties to those of conventional enzymes. Several halophilic hydrolases have been described, including amylases, lipases and proteases, and then used for biotechnological applications. Moreover, the discovery of biopolymer-degrading enzymes offers a new solution for the treatment of oilfield waste, where high temperature and salinity are typically found, while providing valuable information about heterotrophic processes in saline environments. In this work, we describe the results obtained in different screening programs specially focused on the diversity of halophiles showing hydrolytic activities in saline and hypersaline habitats, including the description of enzymes with special biochemical properties. The intracellular lipolytic enzyme LipBL, produced by the moderately halophilic bacterium Marinobacter lipolyticus, showed advantages over other lipases, being an enzyme active over a wide range of pH values and temperatures. The immobilized LipBL derivatives obtained and tested in regio- and enantioselective reactions, showed an excellent behavior in the production of free polyunsaturated fatty acids (PUFAs). On the other hand, the extremely halophilic bacterium, Salicola marasensis sp. IC10 showing lipase and protease activities, was studied for its ability to produce promising enzymes in terms of its resistance to temperature and salinity. PMID:25371331

  11. Halophilic Bacteria as a Source of Novel Hydrolytic Enzymes

    Directory of Open Access Journals (Sweden)

    Encarnación Mellado

    2013-01-01

    Full Text Available Hydrolases constitute a class of enzymes widely distributed in nature from bacteria to higher eukaryotes. The halotolerance of many enzymes derived from halophilic bacteria can be exploited wherever enzymatic transformations are required to function under physical and chemical conditions, such as in the presence of organic solvents and extremes in temperature and salt content. In recent years, different screening programs have been performed in saline habitats in order to isolate and characterize novel enzymatic activities with different properties to those of conventional enzymes. Several halophilic hydrolases have been described, including amylases, lipases and proteases, and then used for biotechnological applications. Moreover, the discovery of biopolymer-degrading enzymes offers a new solution for the treatment of oilfield waste, where high temperature and salinity are typically found, while providing valuable information about heterotrophic processes in saline environments. In this work, we describe the results obtained in different screening programs specially focused on the diversity of halophiles showing hydrolytic activities in saline and hypersaline habitats, including the description of enzymes with special biochemical properties. The intracellular lipolytic enzyme LipBL, produced by the moderately halophilic bacterium Marinobacter lipolyticus, showed advantages over other lipases, being an enzyme active over a wide range of pH values and temperatures. The immobilized LipBL derivatives obtained and tested in regio- and enantioselective reactions, showed an excellent behavior in the production of free polyunsaturated fatty acids (PUFAs. On the other hand, the extremely halophilic bacterium, Salicola marasensis sp. IC10 showing lipase and protease activities, was studied for its ability to produce promising enzymes in terms of its resistance to temperature and salinity.

  12. Enzymic synthesis and hydrolytic resolution of alkyl beta-D-glucopyranosides

    Czech Academy of Sciences Publication Activity Database

    Zarevúcka, M.; Wimmer, Z.; Rejzek, M.; Huňková, Zdenka; Křen, Vladimír

    2001-01-01

    Roč. 23, - (2001), s. 1505-1515 ISSN 0141-5492 R&D Projects: GA ČR GA303/99/1382 Keywords : absolute configuration * diastereoisomeric purity * glucosidases Subject RIV: EE - Microbiology, Virology Impact factor: 0.915, year: 2001

  13. Enzymic synthesis and hydrolytic resolution of alkyl á-D-glucopyranosides

    Czech Academy of Sciences Publication Activity Database

    Zarevúcka, Marie; Wimmer, Zdeněk; Rejzek, Martin; Huňková, Zdenka; Křen, Vladimír

    2001-01-01

    Roč. 23, - (2001), s. 1505-1515 ISSN 0141-5492 R&D Projects: GA ČR GA303/99/1382; GA MŠk OC D10.10 Institutional research plan: CEZ:AV0Z4055905 Keywords : absolute configuration Subject RIV: CE - Biochemistry Impact factor: 0.915, year: 2001

  14. Clickable prodrugs bearing potent and hydrolytically cleavable nicotinamide phosphoribosyltransferase inhibitors

    Directory of Open Access Journals (Sweden)

    Sadrerafi K

    2018-04-01

    Full Text Available Keivan Sadrerafi, Emilia O Mason, Mark W Lee Jr Department of Chemistry, University of Missouri, Columbia, MO, USA Purpose: Our previous study indicated that carborane containing small-molecule 1-(hydroxymethyl-7-(4′-(trans-3″-(3‴-pyridylacrylamidobutyl-1,7-dicarbadodecaborane (hm-MC4-PPEA, was a potent inhibitor of nicotinamide phosphoribosyltransferase (Nampt. Nampt has been shown to be upregulated in most cancers and is a promising target for the treatment of many different types of cancers, including breast cancers. Patients and methods: To increase the selectivity of hm-MC4-PPEA toward cancer cells, three prodrugs were synthesized with different hydrolyzable linkers: ester, carbonate, and carbamate. Using click chemistry a fluorophore was attached to these prodrugs to act as a model for our conjugation strategy and to serve as an aid for prodrug stability studies. The stabilities of these drug conjugates were tested in phosphate-buffered saline (PBS at normothermia (37°C using three different pH levels, 5.5, 7.5, and 9.5, as well as in horse serum at physiological pH. The stability of each was monitored using reversed-phase HPLC equipped with both diode array and fluorescence detection. The inhibitory activity of hm-MC4-PPEA was also measured using a commercially available colorimetric assay. The biological activities of the drug conjugates as well as those of the free drug (hm-MC4-PPEA, were evaluated using the MTT assay against the human breast cancer cell lines T47D and MCF7, as well as the noncancerous, transformed, Nampt-dependent human breast epithelium cell line 184A1.Results: hm-MC4-PPEA showed to be a potent inhibitor of recombinant Nampt activity, exhibiting an IC50 concentration of 6.8 nM. The prodrugs showed great stability towards hydrolytic degradation under neutral, mildly acidic and mildly basic conditions. The carbamate prodrug also showed to be stable in rat serum. However, the carbonate and the ester prodrug

  15. Hydrolytic hydrogen generation using milled aluminum in water activated by Li, In, and Zn additives

    Energy Technology Data Exchange (ETDEWEB)

    Fan, M.Q.; Liu, S.; Wang, C.; Chen, D.; Shu, K.Y. [Department of Materials Science and Engineering, China Jiliang University, Hangzhou (China)

    2012-08-15

    A method for obtaining hydrogen through the hydrolytic reaction of highly activated aluminum (Al) alloy is investigated. The optimized Al-3 wt.% Li-4 wt.% In-7 wt.% Zn alloy significantly improves the maximum hydrogen generation rate and amount (137 mL g{sup -1} min{sup -1} and 1,243 mL g{sup -1}, respectively). An efficiency of 100% was reached within 1 h at 298 K. The synergistic catalytic effects of Li, In, and Zn, which stimulated Al hydrolysis through the formation of micro galvanic cells of In-Li and Al-In-Zn alloys in water, were observed. The reactions were analyzed using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and hydrolytic experiments. The In-Li alloy functions as an initial active center and produces LiOH in water, which further stimulates and changes the hydrolytic process of the Al-In-Zn alloy. The effects of alloy composition, milling time, and hydrolytic temperature were considered and discussed. The results indicate that the hydrolytic reaction of Al-Li-In-Zn alloy in water might be feasible for the production of inexpensive, pure, and safe hydrogen for micro fuel cells. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. A novel method to control hydrolytic degradation of nanocomposite biocompatible materials via imparting superhydrophobicity

    Energy Technology Data Exchange (ETDEWEB)

    Khakbaz, Mobina [Department of Chemical Engineering, Islamic Azad University, Shahrood Branch, P.O. Box 36155-163, Shahrood (Iran, Islamic Republic of); Hejazi, Iman [Department of Polymer Engineering & Color Technology, Amirkabir University of Technology, Tehran (Iran, Islamic Republic of); Seyfi, Javad, E-mail: Jseyfi@gmail.com [Department of Chemical Engineering, Islamic Azad University, Shahrood Branch, P.O. Box 36155-163, Shahrood (Iran, Islamic Republic of); Jafari, Seyed-Hassan [School of Chemical Engineering, University of Tehran, P.O. Box 11155-4563, Tehran (Iran, Islamic Republic of); Khonakdar, Hossein Ali [Iran Polymer and Petrochemical Institute, P.O. Box 14965/115, Tehran (Iran, Islamic Republic of); Davachi, Seyed Mohammad [School of Chemical Engineering, University of Tehran, P.O. Box 11155-4563, Tehran (Iran, Islamic Republic of)

    2015-12-01

    Highlights: • Superhydrophobic surface was obtained from a terpolymer for biomedical applications. • Hydrolytic degradation was delayed notably through inducing superhydrophobicity. • A novel method including combined use of non-solvent and nanoparticles was used. • Extreme wettabilities are attained by varying non-solvent and nanoparticles content. • Use of nanoparticle increased pore size via accelerating the evaporation process. - Abstract: Acceleration of hydrolytic degradation of biomedical materials is not always desirable. For instance, terpolymers based on L-lactide, glycolide and trimethylene carbonate exhibit very fast hydrolytic degradation due to their amorphous structure, hydrophilicity, and high water absorption capability. Therefore, an attempt was made in the current study to impede the hydrolytic degradation for these materials through imparting superhydrophobicity to their surfaces. The used terpolymer has been shown to have promising potential applications as bio-absorbable surgical sutures and other biomedical materials, and thus, its applicability could be further extended upon impeding its hydrolytic degradation. Moreover, a novel method including combined use of non-solvent and nanoparticles was utilized to achieve superhydrophobicity. Very diverse wettability results were obtained which were attributed to the obtained various morphologies according to scanning electron microscopy results. More importantly, a unique hierarchical morphology was found to be responsible for the observed water repellent behavior. X-ray photoelectron spectroscopy results revealed co-existence of nanosilica particles and terpolymer chains on the surface's top layer. Finally, it was found that the superhydrophobic sample exhibited a significantly impeded hydrolytic degradation as compared with the hydrophilic pure terpolymer which was attributed to the formation of air pockets on the surface's top layer.

  17. Hydrolytic and ligninolytic enzyme activities in the Pb contaminated soil inoculated with litter-decomposing fungi.

    Science.gov (United States)

    Kähkönen, Mika A; Lankinen, Pauliina; Hatakka, Annele

    2008-06-01

    The impact of Pb contamination was tested to five hydrolytic (beta-glucosidase, beta-xylosidase, beta-cellobiosidase, alpha-glucosidase and sulphatase) and two ligninolytic (manganese peroxidase, MnP and laccase) enzyme activities in the humus layer in the forest soil. The ability of eight selected litter-degrading fungi to grow and produce extracellular enzymes in the heavily Pb (40 g Pb of kg ww soil(-1)) contaminated and non-contaminated soil in the non-sterile conditions was also studied. The Pb content in the test soil was close to that of the shooting range at Hälvälä (37 g Pb of kg ww soil(-1)) in Southern Finland. The fungi were Agaricus bisporus, Agrocybe praecox, Gymnopus peronatus, Gymnopilus sapineus, Mycena galericulata, Gymnopilus luteofolius, Stropharia aeruginosa and Stropharia rugosoannulata. The Pb contamination (40 g Pb of kg ww soil(-1)) was deleterious to all five studied hydrolytic enzyme activities after five weeks of incubation. All five hydrolytic enzyme activities were significantly higher in the soil than in the extract of the soil indicating that a considerable part of enzymes were particle bound in the soils. Hydrolytic enzyme activities were higher in the non-contaminated soil than in the Pb contaminated soil. Fungal inocula increased the hydrolytic enzyme activities beta-cellobiosidase and beta-glucosidase in non-contaminated soils. All five hydrolytic enzyme activities were similar with fungi and without fungi in the Pb contaminated soil. This was in line that Pb contamination (40 g Pb of kg ww soil(-1)) depressed the growth of all fungi compared to those grown without Pb in the soil. Laccase and MnP activities were low in both Pb contaminated and non-contaminated soil cultures. MnP activities were higher in soil cultures containing Pb than without Pb. Our results showed that Pb in the shooting ranges decreased fungal growth and microbial functioning in the soil.

  18. Hydrolytic stability of polycarbonate-based polyurethane elastomers tested in physiologically simulated conditions

    Czech Academy of Sciences Publication Activity Database

    Serkis, Magdalena; Špírková, Milena; Poreba, Rafal; Hodan, Jiří; Kredatusová, Jana; Kubies, Dana

    2015-01-01

    Roč. 119, September (2015), s. 23-34 ISSN 0141-3910 R&D Projects: GA ČR(CZ) GA13-06700S Institutional support: RVO:61389013 Keywords : polyurethane * elastomer * hydrolytic stability Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.120, year: 2015

  19. Quantitative iTRAQ secretome analysis of aspergillus niger reveals novel hydrolytic enzymes

    NARCIS (Netherlands)

    Adav, S.S.; Li, A.A.; Manavalan, A.; Punt, P.; Sze, S.K.

    2010-01-01

    The natural lifestyle of Aspergillus niger made them more effective secretors of hydrolytic proteins and becomes critical when this species were exploited as hosts for the commercial secretion of heterologous proteins. The protein secretion profile of A. niger and its mutant at different pH was

  20. Metal-ion complexes of functionalised 1,10-Phenanthrolines as hydrolytic synzymes

    NARCIS (Netherlands)

    Weijnen, J.G.J.

    1993-01-01

    In this thesis metal-ion complexes of functionalised 1,10-phenanthroline derivatives have been studied as model systems for hydrolytic metallo-enzymes. Amphiphilic metallo- complexes incorporated into micelles or vesicles and water-soluble complexes in pure aqueous buffer solutions, have

  1. Production of certain hydrolytic enzymes by psychrophilic bacteria from the Antarctic krill, zooplankton and seawater

    Digital Repository Service at National Institute of Oceanography (India)

    Ramaiah, N.

    of hydrolytic enzymes compared to those strains collected either from water or krill samples. Based on these results, the functional role of bacterial enzymes in relation to trophodynamics of euphausiids and their role in the post-harvest technology of krill...

  2. Total Synthesis and Stereochemical Assignment of Delavatine A: Rh-Catalyzed Asymmetric Hydrogenation of Indene-Type Tetrasubstituted Olefins and Kinetic Resolution through Pd-Catalyzed Triflamide-Directed C-H Olefination.

    Science.gov (United States)

    Zhang, Zhongyin; Wang, Jinxin; Li, Jian; Yang, Fan; Liu, Guodu; Tang, Wenjun; He, Weiwei; Fu, Jian-Jun; Shen, Yun-Heng; Li, Ang; Zhang, Wei-Dong

    2017-04-19

    Delavatine A (1) is a structurally unusual isoquinoline alkaloid isolated from Incarvillea delavayi. The first and gram-scale total synthesis of 1 was accomplished in 13 steps (the longest linear sequence) from commercially available starting materials. We exploited an isoquinoline construction strategy and developed two reactions, namely Rh-catalyzed asymmetric hydrogenation of indene-type tetrasubstituted olefins and kinetic resolution of β-alkyl phenylethylamine derivatives through Pd-catalyzed triflamide-directed C-H olefination. The substrate scope of the first reaction covered unfunctionalized olefins and those containing polar functionalities such as sulfonamides. The kinetic resolution provided a collection of enantioenriched indane- and tetralin-based triflamides, including those bearing quaternary chiral centers. The selectivity factor (s) exceeded 100 for a number of substrates. These reactions enabled two different yet related approaches to a key intermediate 28 in excellent enantiopurity. In the synthesis, the triflamide served as not only an effective directing group for C-H bond activation but also a versatile functional group for further elaborations. The relative and absolute configurations of delavatine A were unambiguously assigned by the syntheses of the natural product and its three stereoisomers. Their cytotoxicity against a series of cancer cell lines was evaluated.

  3. Inhibition and kinetic studies of cellulose- and hemicellulose-degrading enzymes of Ganoderma boninense by naturally occurring phenolic compounds.

    Science.gov (United States)

    Surendran, A; Siddiqui, Y; Ali, N S; Manickam, S

    2018-06-01

    Ganoderma sp, the causal pathogen of the basal stem rot (BSR) disease of oil palm, secretes extracellular hydrolytic enzymes. These play an important role in the pathogenesis of BSR by nourishing the pathogen through the digestion of cellulose and hemicellulose of the host tissue. Active suppression of hydrolytic enzymes secreted by Ganoderma boninense by various naturally occurring phenolic compounds and estimation of their efficacy on pathogen suppression is focused in this study. Ten naturally occurring phenolic compounds were assessed for their inhibitory effect on the hydrolytic enzymes of G. boninense. The enzyme kinetics (V max and K m ) and the stability of the hydrolytic enzymes were also characterized. The selected compounds had shown inhibitory effect at various concentrations. Two types of inhibitions namely uncompetitive and noncompetitive were observed in the presence of phenolic compounds. Among all the phenolic compounds tested, benzoic acid was the most effective compound suppressive to the growth and production of hydrolytic enzymes secreted by G. boninense. The phenolic compounds as inhibitory agents can be a better replacement for the metal ions which are known as conventional inhibitors till date. The three hydrolytic enzymes were stable in a wide range of pH and temperature. These findings highlight the efficacy of the applications of phenolic compounds to control Ganoderma. The study has proved a replacement for chemical controls of G. boninense with naturally occurring phenolic compounds. © 2018 The Society for Applied Microbiology.

  4. A faster, high resolution, mtPA-GFP-based mitochondrial fusion assay acquiring kinetic data of multiple cells in parallel using confocal microscopy.

    Science.gov (United States)

    Lovy, Alenka; Molina, Anthony J A; Cerqueira, Fernanda M; Trudeau, Kyle; Shirihai, Orian S

    2012-07-20

    Mitochondrial fusion plays an essential role in mitochondrial calcium homeostasis, bioenergetics, autophagy and quality control. Fusion is quantified in living cells by photo-conversion of matrix targeted photoactivatable GFP (mtPAGFP) in a subset of mitochondria. The rate at which the photoconverted molecules equilibrate across the entire mitochondrial population is used as a measure of fusion activity. Thus far measurements were performed using a single cell time lapse approach, quantifying the equilibration in one cell over an hour. Here, we scale up and automate a previously published live cell method based on using mtPAGFP and a low concentration of TMRE (15 nm). This method involves photoactivating a small portion of the mitochondrial network, collecting highly resolved stacks of confocal sections every 15 min for 1 hour, and quantifying the change in signal intensity. Depending on several factors such as ease of finding PAGFP expressing cells, and the signal of the photoactivated regions, it is possible to collect around 10 cells within the 15 min intervals. This provides a significant improvement in the time efficiency of this assay while maintaining the highly resolved subcellular quantification as well as the kinetic parameters necessary to capture the detail of mitochondrial behavior in its native cytoarchitectural environment. Mitochondrial dynamics play a role in many cellular processes including respiration, calcium regulation, and apoptosis. The structure of the mitochondrial network affects the function of mitochondria, and the way they interact with the rest of the cell. Undergoing constant division and fusion, mitochondrial networks attain various shapes ranging from highly fused networks, to being more fragmented. Interestingly, Alzheimer's disease, Parkinson's disease, Charcot Marie Tooth 2A, and dominant optic atrophy have been correlated with altered mitochondrial morphology, namely fragmented networks. Often times, upon fragmentation

  5. Hydrolytic study of the copolymer Poly pyrrole/ Polyethyleneglycol and Poly pyrrole synthesized by plasma

    International Nuclear Information System (INIS)

    Colin, E.; Enriquez, M.A.; Olayo, M.G.; Cruz, G.J.; Carapia, L.; Romero, M.; Morales, J.; Olayo, R.

    2006-01-01

    In this work the study about the hydrolytic compatibility of semiconductor polymers, copolymer Poly pyrrole/ Polyethyleneglycol (PPy/PEG) and Poly pyrrole (PPy) for their possible use as biomaterials. The polymers were synthesized by plasma between 10 and 100 W, with discharges of splendor RF to 13.5 MHz with resistive coupling. The hydrolytic affinity was evaluated calculating the contact angle with solutions of NaCl, NaCl-MgSO 4 and Krebs-Ringer. The results show a hydrophilicity increment due to the increase of the surface ruggedness with the synthesis energy. On the contrary, the crystallinity diminishes when increasing the power in PPy and it stays approximately constant in PPy/PEG. The electric conductivity presents a growth from 2 to 4 magnitude orders in function of the water content in the polymers. (Author)

  6. Replacement of traditional seawater-soluble pigments by starch and hydrolytic enzymes in polishing antifouling coatings

    DEFF Research Database (Denmark)

    Olsen, Søren Martin; Pedersen, L. T.; Dam-Johansen, Kim

    2010-01-01

    The use of starch and hydrolytic enzymes as replacement for traditional polishing pigments (e.g., Cu2O and ZnO) in antifouling coatings has been investigated. The enzymes facilitate a slow conversion of water-insoluble starch into water-soluble glucose, and dissolution of glucose causes the devel......The use of starch and hydrolytic enzymes as replacement for traditional polishing pigments (e.g., Cu2O and ZnO) in antifouling coatings has been investigated. The enzymes facilitate a slow conversion of water-insoluble starch into water-soluble glucose, and dissolution of glucose causes...... the development of a leached (porous) layer in the wetted, outermost part of the coating. Subsequent water-binder interaction at the pore walls gives rise to polishing, in a manner similar to that of conventional antifouling coatings. Different starch types have been evaluated and classified as potential coating...

  7. Physico-chemical and thermochemical studies of the hydrolytic conversion of amorphous tricalcium phosphate into apatite

    International Nuclear Information System (INIS)

    Somrani, Saida; Banu, Mihai; Jemal, Mohamed; Rey, Christian

    2005-01-01

    The conversion of amorphous tricalcium phosphate with different hydration ratio into apatite in water at 25 deg. C has been studied by microcalorimetry and several physical-chemical methods. The hydrolytic transformation was dominated by two strong exothermic events. A fast, relatively weak, wetting process and a very slow but strong heat release assigned to a slow internal rehydration and the crystallization of the amorphous phase into an apatite. The exothermic phenomenon related to the rehydration exceeded the crystalline transformation enthalpy. Rehydration occurred before the conversion of the amorphous phase into apatite and determined the advancement of the hydrolytic reaction. The apatitic phases formed evolved slightly with time after their formation. The crystallinity increased whereas the amount of HPO 4 2- ion decreased. These data allow a better understanding of the behavior of biomaterials involving amorphous phases such as hydroxyapatite plasma-sprayed coatings

  8. Variation in pH Optima of Hydrolytic Enzyme Activities in Tropical Rain Forest Soils ▿

    OpenAIRE

    Turner, Benjamin L.

    2010-01-01

    Extracellular enzymes synthesized by soil microbes play a central role in the biogeochemical cycling of nutrients in the environment. The pH optima of eight hydrolytic enzymes involved in the cycles of carbon, nitrogen, phosphorus, and sulfur, were assessed in a series of tropical forest soils of contrasting pH values from the Republic of Panama. Assays were conducted using 4-methylumbelliferone-linked fluorogenic substrates in modified universal buffer. Optimum pH values differed markedly am...

  9. Improved performance of Yarrowia lipolytica lipase-catalyzed kinetic resolution of (R,S)-2-octanol by an integrated strategy of interfacial activation, bioimprinting and immobilization.

    Science.gov (United States)

    Liu, Ying; Guo, Chen; Sun, Xi-Tong; Liu, Chun-Zhao

    2013-08-01

    Yarrowia lipolytica lipase (YLL) demonstrated an (R)-enantiopreference for efficient resolution of (R,S)-2-octanol. The activity, enantioselectivity, the ratio of substrate to enzyme, acetaldehyde tolerance, and operational stability of YLL were improved by an integrated strategy of interfacial activation, bioimprinting, and immobilization. In comparison with the control, both the enzymatic activity and enantioselectivity increased by a factor of 8.85 and 2.75 by the integrated strategy, respectively. Fifty-one percentage of conversion with 220 of enantioselectivity was obtained using the immobilized YLL prepared by the integrated strategy at a ratio of 104 of substrate to enzyme loaded. The immobilized YLL retained 97% of its initial activity without a decrease in enantioselectivity after 10 successive reuse cycles. Together these results will result in a promising strategy with the YYL for efficient resolution of (R,S)-2-octanol in practice. Copyright © 2013 Elsevier Ltd. All rights reserved.

  10. Tribological study of a highly hydrolytically stable phenylboronic acid ester containing benzothiazolyl in mineral oil

    International Nuclear Information System (INIS)

    Li, Zhipeng; Li, Xiufeng; Zhang, Yawen; Ren, Tianhui; Zhao, Yidong; Zeng, Xiangqiong; Heide, E. van der

    2014-01-01

    A novel long chain alkyl phenylboronic acid ester containing heterocyclic compound, bis (1-(benzothiazol-2-ylthio) propan-2-yl)-4-dodecylphenylboronic acid ester (DBBMT), was synthesized and characterized. The hydrolytic stability of the DBBMT was evaluated and the results show that DBBMT is of outstanding hydrolytic stability compared with normal borate esters, which indicates that the designed molecular structure, by introducing benzene ring to conjugate with the electron-deficient boron and the benzothiazole as a hinder group, is effective on obtaining a hydrolytically stable long chain alkyl phenylboronic acid ester. The tribological properties of DBBMT and ZDDP in mineral base oil were evaluated using a four-ball tribometer, which suggests that the DBBMT possesses comprehensive tribological properties and could be a potential candidate for the replacement of ZDDP. Furthermore, in order to understand the tribological behaviors, the worn surface was analyzed by X-ray photoelectron spectroscopy (XPS) and X-ray absorption near edge structure (XANES) spectroscopy. The results indicate that the elements S, B, O and Fe perform complicated tribochemical reactions to form the compact tribological film composed of B 2 O 3 , FeS, Fe 3 O 4 and FeSO 4 .

  11. Durability of switchable QR code carriers under hydrolytic and photolytic conditions

    International Nuclear Information System (INIS)

    Ecker, Melanie; Pretsch, Thorsten

    2013-01-01

    Following a guest diffusion approach, the surface of a shape memory poly(ester urethane) (PEU) was either black or blue colored. Bowtie-shaped quick response (QR) code carriers were then obtained from laser engraving and cutting, before thermo-mechanical functionalization (programming) was applied to stabilize the PEU in a thermo-responsive (switchable) state. The stability of the dye within the polymer surface and long-term functionality of the polymer were investigated against UVA and hydrolytic ageing. Spectrophotometric investigations verified UVA ageing-related color shifts from black to yellow-brownish and blue to petrol-greenish whereas hydrolytically aged samples changed from black to greenish and blue to light blue. In the case of UVA ageing, color changes were accompanied by dye decolorization, whereas hydrolytic ageing led to contrast declines due to dye diffusion. The Michelson contrast could be identified as an effective tool to follow ageing-related contrast changes between surface-dyed and laser-ablated (undyed) polymer regions. As soon as the Michelson contrast fell below a crucial value of 0.1 due to ageing, the QR code was no longer decipherable with a scanning device. Remarkably, the PEU information carrier base material could even then be adequately fixed and recovered. Hence, the surface contrast turned out to be the decisive parameter for QR code carrier applicability. (paper)

  12. Scanning electron microscopic study of the hydrolytic degradation of poly(glycolic acid) suture

    International Nuclear Information System (INIS)

    Chu, C.C.; Campbell, N.D.

    1982-01-01

    This article reports the morphological observations on the surface changes of poly-(glycolic acid) sutures which have been exposed to various dosages of gamma irradiation (0, 2.5, 5.0, 10, 20 and 40 Mrad) and duration of immersion (0, 7, 14, 28, 48, 60, and 90 days) in a physiological saline buffer. The most important gross morphological characteristics of PGA suture hydrolytic degradation is the formation of surface cracks on the filaments. The regularity of the surface cracks increased with an increase in the gamma irradiation and the duration of hydrolysis. Surface cracks were not observed in irradiated sutures that had not been subjected to hydrolytic degradation. The arrangement of the surface cracks, their orientation on the filaments, and the direction of crack propagation provide very useful information for depicting the mechanism of hydrolytic degradation in this class of fibrous material. The microfibrillar model of fiber structure has been used as the basis for the proposed degradation mechanism of PGA in vitro. It is believed that hydrolysis occurs initially in the amorphous regions sandwiched between two crystalline zones, as tie-chain segments, free chain ends, and chain folds in these regions degrade into fragments. As degradation proceeds, the size of the fragments reaches the stage at which they can be dissolved into the buffer medium. This dissolution removes the fragments from the amorphous regions, and surface cracks appeared

  13. Substrate-Wrapped, Single-Walled Carbon Nanotube Probes for Hydrolytic Enzyme Characterization.

    Science.gov (United States)

    Kallmyer, Nathaniel E; Musielewicz, Joseph; Sutter, Joel; Reuel, Nigel F

    2018-04-17

    Hydrolytic enzymes are a topic of continual study and improvement due to their industrial impact and biological implications; however, the ability to measure the activity of these enzymes, especially in high-throughput assays, is limited to an established, few enzymes and often involves the measurement of secondary byproducts or the design of a complex degradation probe. Herein, a versatile single-walled carbon nanotube (SWNT)-based biosensor that is straightforward to produce and measure is described. The hydrolytic enzyme substrate is rendered as an amphiphilic polymer, which is then used to solubilize the hydrophobic nanotubes. When the target enzyme degrades the wrapping, the SWNT fluorescent signal is quenched due to increased solvent accessibility and aggregation, allowing quantitative measurement of hydrolytic enzyme activity. Using (6,5) chiral SWNT suspended with polypeptides and polysaccharides, turnover frequencies are estimated for cellulase, pectinase, and bacterial protease. Responses are recorded for concentrations as low as 5 fM using a well-characterized protease, Proteinase K. An established trypsin-based plate reader assay is used to compare this nanotube probe assay with standard techniques. Furthermore, the effect of freeze-thaw cycles and elevated temperature on enzyme activity is measured, suggesting freezing to have minimal impact even after 10 cycles and heating to be detrimental above 60 °C. Finally, rapid optimization of enzyme operating conditions is demonstrated by generating a response surface of cellulase activity with respect to temperature and pH to determine optimal conditions within 2 h of serial scans.

  14. The Power of Non-Hydrolytic Sol-Gel Chemistry: A Review

    Directory of Open Access Journals (Sweden)

    Ales Styskalik

    2017-05-01

    Full Text Available This review is devoted to non-hydrolytic sol-gel chemistry. During the last 25 years, non-hydrolytic sol-gel (NHSG techniques were found to be attractive and versatile methods for the preparation of oxide materials. Compared to conventional hydrolytic approaches, the NHSG route allows reaction control at the atomic scale resulting in homogeneous and well defined products. Due to these features and the ability to design specific materials, the products of NHSG reactions have been used in many fields of application. The aim of this review is to present an overview of NHSG research in recent years with an emphasis on the syntheses of mixed oxides, silicates and phosphates. The first part of the review highlights well known condensation reactions with some deeper insights into their mechanism and also presents novel condensation reactions established in NHSG chemistry in recent years. In the second section we discuss porosity control and novel compositions of selected materials. In the last part, the applications of NHSG derived materials as heterogeneous catalysts and supports, luminescent materials and electrode materials in Li-ion batteries are described.

  15. Durability of switchable QR code carriers under hydrolytic and photolytic conditions

    Science.gov (United States)

    Ecker, Melanie; Pretsch, Thorsten

    2013-09-01

    Following a guest diffusion approach, the surface of a shape memory poly(ester urethane) (PEU) was either black or blue colored. Bowtie-shaped quick response (QR) code carriers were then obtained from laser engraving and cutting, before thermo-mechanical functionalization (programming) was applied to stabilize the PEU in a thermo-responsive (switchable) state. The stability of the dye within the polymer surface and long-term functionality of the polymer were investigated against UVA and hydrolytic ageing. Spectrophotometric investigations verified UVA ageing-related color shifts from black to yellow-brownish and blue to petrol-greenish whereas hydrolytically aged samples changed from black to greenish and blue to light blue. In the case of UVA ageing, color changes were accompanied by dye decolorization, whereas hydrolytic ageing led to contrast declines due to dye diffusion. The Michelson contrast could be identified as an effective tool to follow ageing-related contrast changes between surface-dyed and laser-ablated (undyed) polymer regions. As soon as the Michelson contrast fell below a crucial value of 0.1 due to ageing, the QR code was no longer decipherable with a scanning device. Remarkably, the PEU information carrier base material could even then be adequately fixed and recovered. Hence, the surface contrast turned out to be the decisive parameter for QR code carrier applicability.

  16. Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform

    OpenAIRE

    Lundberg, Pontus; Lee, Bongjae F.; van den Berg, Sebastiaan A.; Pressly, Eric D.; Lee, Annabelle; Hawker, Craig J.; Lynd, Nathaniel A.

    2012-01-01

    A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxi...

  17. New signal acquisition and processing system for the execution of initial criticality after refueling and physical tests at low power in Angra-2, with the incorporation of the real time resolution of the inverse point kinetic equation - IPK

    Energy Technology Data Exchange (ETDEWEB)

    Júnior, Décio Brandes M.F.; Oliveira, Mônica Georgia N.; Silva, Cristiano da, E-mail: deciobr@eletronuclear.gov.br, E-mail: mongeor@eletronuclear.gov.br, E-mail: cdsilva@eletronuclear.gov.br [Eletrobrás Termonuclear S.A. (ELETRONUCLEAR), Angra dos Reis, RJ (Brazil). Departamento DDD.O - Física de Reatores

    2017-07-01

    The goal of this work is present the new System of Acquisition and Signal Processing for the execution of the initial criticality after refueling and physical tests at low power with the incorporation of the real time resolution of Inverse Point Kinetic Equations (IPK). The system was developed using cRIO 9082 hardware (compactRIO), which is a programmable logic controller (PLC) and, the National Lab's LabVIEW programming language. The developed system enabled a better visualization and monitoring interface of the neutron flux evolution during the first criticality of cycle and following the low power physical tests, which allows the Reactor Physics Group and Reactor Operators of Angra 2 guide faster and accurately the reactivity variations at physical tests. The digital reactivity meter developed reinforces in Angra-2 the set of operational practices of reactivity management. (author)

  18. Asymmetric aminolytic kinetic resolution of racemic epoxides using recyclable chiral polymeric Co(III)-salen complexes: a protocol for total utilization of racemic epoxide in the synthesis of (R)-Naftopidil and (S)-Propranolol.

    Science.gov (United States)

    Kumar, Manish; Kureshy, Rukhsana I; Shah, Arpan K; Das, Anjan; Khan, Noor-ul H; Abdi, Sayed H R; Bajaj, Hari C

    2013-09-20

    Chiral polymeric Co(III) salen complexes with chiral ((R)/(S)-BINOL, diethyl tartrate) and achiral (piperazine and trigol) linkers with varying stereogenic centers were synthesized for the first time and used as catalysts for aminolytic kinetic resolution (AKR) of a variety of terminal epoxides and glycidyl ethers to get enantio-pure epoxides (ee, 99%) and N-protected β-amino alcohols (ee, 99%) with quantitative yield in 16 h at RT under optimized reaction conditions. This protocol was also used for the synthesis of two enantiomerically pure drug molecules (R)-Naftopidil (α1-blocker) and (S)-Propranolol (β-blocker) as a key step via AKR of single racemic naphthylglycidyl ether with Boc-protected isoproylamine with 100% epoxide utilization at 1 g level. The catalyst 1 was successfully recycled for a number of times.

  19. New signal acquisition and processing system for the execution of initial criticality after refueling and physical tests at low power in Angra-2, with the incorporation of the real time resolution of the inverse point kinetic equation - IPK

    International Nuclear Information System (INIS)

    Júnior, Décio Brandes M.F.; Oliveira, Mônica Georgia N.; Silva, Cristiano da

    2017-01-01

    The goal of this work is present the new System of Acquisition and Signal Processing for the execution of the initial criticality after refueling and physical tests at low power with the incorporation of the real time resolution of Inverse Point Kinetic Equations (IPK). The system was developed using cRIO 9082 hardware (compactRIO), which is a programmable logic controller (PLC) and, the National Lab's LabVIEW programming language. The developed system enabled a better visualization and monitoring interface of the neutron flux evolution during the first criticality of cycle and following the low power physical tests, which allows the Reactor Physics Group and Reactor Operators of Angra 2 guide faster and accurately the reactivity variations at physical tests. The digital reactivity meter developed reinforces in Angra-2 the set of operational practices of reactivity management. (author)

  20. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia

    2014-01-01

    After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images.......After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....

  1. The effect of oxidation on the enzyme-catalyzed hydrolytic biodegradation of poly(urethane)s.

    Science.gov (United States)

    Labow, Rosalind S; Tang, Yiwen; McCloskey, Christopher B; Santerre, J Paul

    2002-01-01

    Although the biodegradation of polyurethanes (PU) by oxidative and hydrolytic agents has been studied extensively, few investigations have reported on the combination of their effects. Since neutrophils (PMN) arrive at an implanted device first and release HOCl, followed by monocyte-derived macrophages (MDM) which have potent esterase activities and oxidants of their own, the combined effect of oxidative and hydrolytic degradation on radiolabeled polycarbonate-polyurethanes (PCNU)s was investigated and compared to that of a polyester-PU (PESU) and a polyether-PU (PEU). The PCNUs were synthesized with PCN (MW = 1,000), and butanediol (14C-BD) and one of two diisocyanates, hexane-1,6-diisocyanate (14C-HDI) or methylene bis-p-phenyl diisocyanate (MDI). The PESU and PEU were synthesized using toluene-diisocyanate (14C-TDI), with polycaprolactone and polytetramethylene oxide as soft segments respectively, and ethylene diamine as the chain extender. The effect of pre-treatment with 0.1 mM HOC1 for 1 week on the HDI-based PCNUs and both TDI-based PUs resulted in a significant inhibition of radiolabel release (RR) elicited by cholesterol esterase (CE), when compared to buffer alone, whereas the MDI-based PCNU showed a small but significant increase. When PMN were activated on the HDI-based PCNU surface with phorbol myristate acetate (PMA), HOCl was released for 3 h, and was almost completely abolished by sodium azide (AZ). Simultaneously, the PMN-elicited RR, shown previously to be due to the esterolytic cleavage by serine proteases, was inhibited approximately 75% by PMA-activation of the cells, but significantly increased relative to the latter when AZ was added. Both in vitro oxidation by HOCl and the release of HOCI by PMN were associated with the inhibition of RR and suggest perturbations between oxidative and hydrolytic mechanisms of biodegradation.

  2. Novel Materials through Non-Hydrolytic Sol-Gel Processing: Negative Thermal Expansion Oxides and Beyond

    Directory of Open Access Journals (Sweden)

    Cora Lind

    2010-04-01

    Full Text Available Low temperature methods have been applied to the synthesis of many advanced materials. Non-hydrolytic sol-gel (NHSG processes offer an elegant route to stable and metastable phases at low temperatures. Excellent atomic level homogeneity gives access to polymorphs that are difficult or impossible to obtain by other methods. The NHSG approach is most commonly applied to the preparation of metal oxides, but can be easily extended to metal sulfides. Exploration of experimental variables allows control over product stoichiometry and crystal structure. This paper reviews the application of NHSG chemistry to the synthesis of negative thermal expansion oxides and selected metal sulfides.

  3. Fungal strains as catalysts for the biotransformation of halolactones by hydrolytic dehalogenation with the dimethylcyclohexane system.

    Science.gov (United States)

    Grabarczyk, Małgorzata

    2012-08-14

    Bicyclic chloro-, bromo- and iodo-γ-lactones with dimethylcyclohexane rings were used as substrates for bioconversion by several fungal strains (Fusarium, Botrytis and Beauveria). Most of the selected microorganisms transformed these lactones by hydrolytic dehalogenation into the new compound cis-2-hydroxy-4,6-dimethyl-9-oxabicyclo[4.3.0]- nonan-8-one, mainly the (-)-isomer. When iodo-γ-lactone was used as the substrate, two products were observed: a hydroxy-γ-lactone and an unsaturated lactone. The structures of all substrates and products were established on the basis of their spectral data. The mechanism of dehalogenation of three halolactones was also studied.

  4. Thermogravimetry for optimization of chloride pyro hydrolytic separations in zirconia-magnesia matrix

    International Nuclear Information System (INIS)

    Pires, M.A.F.; Dantas, E.S.K.

    1992-08-01

    A fast and accurate method for chloride ion determination in zirconia-magnesia matrix was studied the method consists in the pyro hydrolysis of the oxides at 900 o C, using a quartz apparatus, during thirty minutes and further determination of the chloride ion collected by means of either ion-selective electrode or ion chromatography. The thermogravimetric curves (TG curves) of the metal oxides and oxychlorides provide all the information about the chloride ion evolution temperature and the influence of pyro hydrolytic accelerators (U 3 O 8 ) on ion evolution. (author)

  5. Hydrolytic potential of a psychrotrophic Pseudomonas isolated from refrigerated raw milk

    Directory of Open Access Journals (Sweden)

    Ana Paula F. Corrêa

    2011-12-01

    Full Text Available The production of extracellular hydrolases by a psychrotrophic bacterium isolated from refrigerated raw milk, and identified as a Pseudomonas sp. belonging to the Pseudomonas jenssenii group, was studied. This bacterium produced proteolytic and lipolytic enzymes in all media investigated (skim milk, cheese whey, casein broth, and tryptone soy broth. High levels of α-glucosidase were produced in skim milk broth. Hydrolytic enzymes detected in skim milk broth are of particular concern, indicating that these enzymes could be produced by Pseudomonas sp. during the cold storage of raw milk, contributing to the spoilage problem in milk and dairy products.

  6. Characterization of hydrolytic degradation of polylactic acid/rice hulls composites in water at different temperatures

    Directory of Open Access Journals (Sweden)

    2011-02-01

    Full Text Available Hydrolytic degradations of polylactic acid/rice hulls (PLA/RH composites with various rice hulls contents due to water absorptions at 23, 51 and 69°C were investigated by studying the thermal properties, chemical composition, molecular weight, and morphology of the degraded products. The results have attested that the stability of PLA/RH composites in water depends slightly on rice hulls contents but it is significantly influenced by water temperature. Water absorption in 30 days at 23°C was between 0.87 and 9.25% depending on rice hull contents. However, at thermophilic temperatures, the water absorption and degradation of these products were increased significantly. Saturations were achieved in less than 25 and 9 days at 51°C and 69°C, respectively, while hydrolytic degradation was demonstrated by an increase in fragility and development of crystallinity. At 69°C, there were significant reductions of the decomposition and glass transition temperatures of the polymer by 13°C. These changes were associated with the reduction of the molecular weight of PLA from 153.1 kDa to ~10.7 kDa due to hydrolysis of its ester group.

  7. Hydrolytic Degradation Behaviors of Poly(p-dioxanone) in Ambient Environments

    Institute of Scientific and Technical Information of China (English)

    You Yuan; Song-dong Ding; Yin-qiao Zhao; Yu-zhong Wang

    2014-01-01

    The effects of temperature and relative humidity on the hydrolytic degradation of poly(p-dioxanone) (PPDO) were investigated.The hydrolytic degradation behaviors were monitored by tracing the changes of water absorption,mechanical and crystalline properties,molecular weight and its distribution,surface morphologies,as well as infrared absorption peaks and hydrogen chemical shifts during the degradation.It is found that the water absorption increases whilst the intrinsic viscosity,tensile strength and elongation at break decrease as the temperature or relative humidity increases.With degradation time growing,the molecular weight drops and its distribution broadens.The crystallinity of PPDO has a tendency to increase at first and then to decrease,while the crystalline structure is not significantly changed.At the same time,some cracks are observed on the surface and keep growing and deepening.All results show that temperature plays more significant roles than relative humidity during the degradation.The analyses of Fourier transform infrared spectroscopy and hydrogen nuclear magnetic resonance spectroscopy reveal that the degradation of PPDO is a predominant hydrolysis of ester linkages.

  8. Reticular Chemistry in Action: A Hydrolytically Stable MOF Capturing Twice Its Weight in Adsorbed Water

    KAUST Repository

    Towsif Abtab, Sk Md; Alezi, Dalal; Bhatt, Prashant; Shkurenko, Aleksander; Belmabkhout, Youssef; Aggarwal, Himanshu; Weselinski, Lukasz Jan; Alsadun, Norah Sadun; Samin, Umer; Hedhili, Mohamed N.; Eddaoudi, Mohamed

    2018-01-01

    Summary Hydrolytically stable adsorbents, with notable water uptake, are of prime importance and offer great potential for many water-adsorption-related applications. Nevertheless, deliberate construction of tunable porous solids with high porosity and high stability remains challenging. Here, we present the successful deployment of reticular chemistry to address this demand: we constructed Cr-soc-MOF-1, a chemically and hydrolytically stable chromium-based metal-organic framework (MOF) with underlying soc topology. Prominently, Cr-soc-MOF-1 offers the requisite thermal and chemical stability concomitant with unique adsorption properties, namely extraordinary high porosity (apparent surface area of 4,549 m2/g) affording a water vapor uptake of 1.95 g/g at 70% relative humidity. This exceptional water uptake is maintained over more than 100 adsorption-desorption cycles. Markedly, the adsorbed water can be fully desorbed by just the simple reduction of the relative humidity at 25°C. Cr-soc-MOF-1 offers great potential for use in applications pertaining to water vapor control in enclosed and confined spaces and dehumidification.

  9. Reticular Chemistry in Action: A Hydrolytically Stable MOF Capturing Twice Its Weight in Adsorbed Water

    KAUST Repository

    Towsif Abtab, Sk Md

    2018-01-11

    Summary Hydrolytically stable adsorbents, with notable water uptake, are of prime importance and offer great potential for many water-adsorption-related applications. Nevertheless, deliberate construction of tunable porous solids with high porosity and high stability remains challenging. Here, we present the successful deployment of reticular chemistry to address this demand: we constructed Cr-soc-MOF-1, a chemically and hydrolytically stable chromium-based metal-organic framework (MOF) with underlying soc topology. Prominently, Cr-soc-MOF-1 offers the requisite thermal and chemical stability concomitant with unique adsorption properties, namely extraordinary high porosity (apparent surface area of 4,549 m2/g) affording a water vapor uptake of 1.95 g/g at 70% relative humidity. This exceptional water uptake is maintained over more than 100 adsorption-desorption cycles. Markedly, the adsorbed water can be fully desorbed by just the simple reduction of the relative humidity at 25°C. Cr-soc-MOF-1 offers great potential for use in applications pertaining to water vapor control in enclosed and confined spaces and dehumidification.

  10. Investigation of the hydrolytic and radiolytic degradation of HEH[EHP

    International Nuclear Information System (INIS)

    Peterman, Dean Richard; McDowell, Rocklan George; Zarzana, Christopher Andrew; Johnson, Kristyn Marie; Rowe, Salene Marie; Groenewold, Gary Steven

    2016-01-01

    The extractant 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP]) is a component used in both the Advanced TALSPEAK and ALSEP solvent extraction processes. The most likely compound formed via hydrolytic or radiolytic degradation of HEH[EHP] would be the phosphonic acid 2-ethylhexylphosphonic acid (H2EHP) that is formed by cleavage of the P-O-R bond. Thus far, attempts to detect H2EHP by gas chromatography or mass spectrometry have not been successful. The inability to detect this proposed degradation product in analytical samples is likely due to inadequate analysis techniques, lack of H2EHP production, further decomposition of H2EHP forming products not detectable by the employed analytical techniques, or a combination of all of the above scenarios. In order to address this problem, commercially available alkylphosphonic acids were acquired and used as surrogates for H2EHP in the gas chromatography and mass spectrometry analysis of samples. Once the ability to detect alkylphosphonic acid compounds was confirmed, these analytical techniques were used to confirm the production of H2EHP in samples of HEH[EHP] exposed to nitric acid and nitric acid plus gamma radiation. This report provides a brief summary of results and serves as documentation of the completion the level four milestone M4FT-16IN030102025 “Investigate the hydrolytic and radiolytic degradation of HEH[EHP]”.

  11. Unfolded protein response is required for Aspergillus oryzae growth under conditions inducing secretory hydrolytic enzyme production.

    Science.gov (United States)

    Tanaka, Mizuki; Shintani, Takahiro; Gomi, Katsuya

    2015-12-01

    Unfolded protein response (UPR) is an intracellular signaling pathway for adaptation to endoplasmic reticulum (ER) stress. In yeast UPR, Ire1 cleaves the unconventional intron of HAC1 mRNA, and the functional Hac1 protein translated from the spliced HAC1 mRNA induces the expression of ER chaperone genes and ER-associated degradation genes for the refolding or degradation of unfolded proteins. In this study, we constructed an ireA (IRE1 ortholog) conditionally expressing strain of Aspergillus oryzae, a filamentous fungus producing a large amount of amylolytic enzymes, and examined the contribution of UPR to ER stress adaptation under physiological conditions. Repression of ireA completely blocked A. oryzae growth under conditions inducing the production of hydrolytic enzymes, such as amylases and proteases. This growth defect was restored by the introduction of unconventional intronless hacA (hacA-i). Furthermore, UPR was observed to be induced by amylolytic gene expression, and the disruption of the transcriptional activator for amylolytic genes resulted in partial growth restoration of the ireA-repressing strain. In addition, a homokaryotic ireA disruption mutant was successfully generated using the strain harboring hacA-i as a parental host. These results indicated that UPR is required for A. oryzae growth to alleviate ER stress induced by excessive production of hydrolytic enzymes. Copyright © 2015 Elsevier Inc. All rights reserved.

  12. A fluorescence-based hydrolytic enzyme activity assay for quantifying toxic effects of Roundup® to Daphnia magna

    DEFF Research Database (Denmark)

    Ørsted, Michael; Roslev, Peter

    2015-01-01

    Daphnia magna is a widely used model organism for aquatic toxicity testing. In the present study, we investigated the hydrolytic enzyme activity of D. magna after exposure to toxicant stress. In vivo enzyme activity was quantified using 15 fluorogenic enzyme probes based on 4-methylumbelliferyl...... or 7-amino-4-methylcoumarin. Probing D. magna enzyme activity was evaluated using short-term exposure (24-48 h) to the reference chemical K2Cr2O7, or the herbicide formulation Roundup®. Toxicant induced changes in hydrolytic enzyme activity were compared to changes in mobility (ISO 6341). The results...... showed that hydrolytic enzyme activity was quantifiable as a combination of whole body fluorescence of D. magna, and fluorescence of the surrounding water. Exposure of D. magna to lethal and sublethal concentrations of Roundup® resulted in loss of whole body enzyme activity, and release of cell...

  13. Crystallization and preliminary X-ray crystallographic study of the wild type and two mutants of the CP1 hydrolytic domain from Aquifex aeolicus leucyl-tRNA synthetase

    Energy Technology Data Exchange (ETDEWEB)

    Cura, Vincent; Olieric, Natacha; Guichard, Alexandre [Département de Biologie et Génomique Structurales, UMR 7104, Institut de Génétique et de Biologie Moléculaire et Cellulaire, CNRS/INSERM/ULP Strasbourg, 1 Rue Laurent Fries, 67404 Illkirch (France); Wang, En-Duo [State Key Laboratory of Molecular Biology, Institute of Biochemistry and Cell Biology, Shanghai Institutes for Biological Sciences, The Chinese Academy of Sciences, 320 Yue Yang Road, Shanghai 200031 (China); Moras, Dino [Département de Biologie et Génomique Structurales, UMR 7104, Institut de Génétique et de Biologie Moléculaire et Cellulaire, CNRS/INSERM/ULP Strasbourg, 1 Rue Laurent Fries, 67404 Illkirch (France); Eriani, Gilbert [Architecture et Réactivité de l’ARN, UPR 9002, Institut de Biologie Moléculaire et Cellulaire du CNRS, 15 Rue René Descartes, 67084 Strasbourg (France); Cavarelli, Jean, E-mail: cava@igbmc.u-strasbg.fr [Département de Biologie et Génomique Structurales, UMR 7104, Institut de Génétique et de Biologie Moléculaire et Cellulaire, CNRS/INSERM/ULP Strasbourg, 1 Rue Laurent Fries, 67404 Illkirch (France)

    2005-10-01

    The wild-type editing CP1 domain of A. aeolicus leucyl-tRNA synthetase and two mutant CP1 domains have been overexpressed, purified and crystallized. X-ray diffraction data have been collected to 1.8 Å, which has enabled determination of the structures by molecular replacement. The editing or hydrolytic CP1 domain of leucyl-tRNA synthetase (LeuRS) hydrolyses several misactivated amino acids. The CP1 domain of Aquifex aeolicus LeuRS was expressed, purified and crystallized by the hanging-drop vapour-diffusion method using ammonium sulfate as precipitant. Crystals belong to space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 38.8, b = 98.4, c = 116.7 Å. Crystals diffract to beyond 1.8 Å resolution and contain two monomers in the asymmetric unit. Two CP1 mutants in which a conserved threonine residue essential for the fidelity of the hydrolytic pathway is mutated to alanine or glutamic acid have also been expressed and crystallized. Crystals of the two CP1 mutants are isomorphs of the wild type and diffract to beyond 1.9 Å resolution. All structures were solved by molecular-replacement techniques.

  14. Crystallization and preliminary X-ray crystallographic study of the wild type and two mutants of the CP1 hydrolytic domain from Aquifex aeolicus leucyl-tRNA synthetase

    International Nuclear Information System (INIS)

    Cura, Vincent; Olieric, Natacha; Guichard, Alexandre; Wang, En-Duo; Moras, Dino; Eriani, Gilbert; Cavarelli, Jean

    2005-01-01

    The wild-type editing CP1 domain of A. aeolicus leucyl-tRNA synthetase and two mutant CP1 domains have been overexpressed, purified and crystallized. X-ray diffraction data have been collected to 1.8 Å, which has enabled determination of the structures by molecular replacement. The editing or hydrolytic CP1 domain of leucyl-tRNA synthetase (LeuRS) hydrolyses several misactivated amino acids. The CP1 domain of Aquifex aeolicus LeuRS was expressed, purified and crystallized by the hanging-drop vapour-diffusion method using ammonium sulfate as precipitant. Crystals belong to space group P2 1 2 1 2 1 , with unit-cell parameters a = 38.8, b = 98.4, c = 116.7 Å. Crystals diffract to beyond 1.8 Å resolution and contain two monomers in the asymmetric unit. Two CP1 mutants in which a conserved threonine residue essential for the fidelity of the hydrolytic pathway is mutated to alanine or glutamic acid have also been expressed and crystallized. Crystals of the two CP1 mutants are isomorphs of the wild type and diffract to beyond 1.9 Å resolution. All structures were solved by molecular-replacement techniques

  15. Physical kinetics

    International Nuclear Information System (INIS)

    Lifschitz, E.M.; Pitajewski, L.P.

    1983-01-01

    The textbook covers the subject under the following headings: kinetic gas theory, diffusion approximation, collisionless plasma, collisions within the plasma, plasma in the magnetic field, theory of instabilities, dielectrics, quantum fluids, metals, diagram technique for nonequilibrium systems, superconductors, and kinetics of phase transformations

  16. Towards early detection of the hydrolytic degradation of poly(bisphenol A)carbonate by hyphenated liquid chromatography and comprehensive two-dimensional liquid chromatography

    NARCIS (Netherlands)

    Coulier, L.; Kaal, E.R.; Hankemeier, Th.

    2006-01-01

    The hydrolytic degradation of poly(bisphenol A)carbonate (PC) has been characterized by various liquid chromatography techniques. Size exclusion chromatography (SEC) showed a significant decrease in molecular mass as a result of hydrolytic degradation, while 'liquid chromatography at critical

  17. Heparin kinetics

    International Nuclear Information System (INIS)

    Swart, C.A.M. de.

    1983-01-01

    The author has studied the kinetics of heparin and heparin fractions after intravenous administration in humans and in this thesis the results of this study are reported. Basic knowledge about the physico-chemical properties of heparin and its interactions with proteins resulting in anticoagulant and lipolytic effects are discussed in a review (chapter II), which also comprises some clinical aspects of heparin therapy. In chapter III the kinetics of the anticoagulant effect are described after intravenous administration of five commercial heparin preparations. A mathematical model is presented that fits best to these kinetics. The kinetics of the anticoagulant and lipolytic effects after intravenous injection of various 35 S-radiolabelled heparin fractions and their relationship with the disappearance of the radiolabel are described in chapter IV. Chapter V gives a description of the kinetics of two radiolabels after injection of in vitro formed complexes consisting of purified, 125 I-radiolabelled antithrombin III and various 35 S-radiolabelled heparin fractions. (Auth.)

  18. [Description of the phylogenetic structure of hydrolytic prokaryotic complex in the soils].

    Science.gov (United States)

    Lukacheva, E G; Chernov, T I; Bykova, E M; Vlasenko, A N; Manucharova, N A

    2013-01-01

    With the help of the molecular-biological method of cell hybridization in situ (FISH), the abundance of a physiologically active hydrolytic prokaryotic complex in chernozem and gley-podzolic soils is determined. The total proportion of metabolically active cells, which were detected by hybridization with universal probes as representatives of the domains Bacteria and Archaea, in samples of the studied soil, was from 38% for chernozem up to 78% for gley-podzolic soil of the total number of cells. The differences in the structure of chitinolytic and pectinolytic prokaryotic soil complexes are detected. Along with the high abundance of Actinobacteria and Firmicutes in the soils with chitin, an increase in phylogenetic groups such as Alphaproteobacteria and Bacteroidetes is observed.

  19. Metagenomics as a Tool for Enzyme Discovery: Hydrolytic Enzymes from Marine-Related Metagenomes.

    Science.gov (United States)

    Popovic, Ana; Tchigvintsev, Anatoly; Tran, Hai; Chernikova, Tatyana N; Golyshina, Olga V; Yakimov, Michail M; Golyshin, Peter N; Yakunin, Alexander F

    2015-01-01

    This chapter discusses metagenomics and its application for enzyme discovery, with a focus on hydrolytic enzymes from marine metagenomic libraries. With less than one percent of culturable microorganisms in the environment, metagenomics, or the collective study of community genetics, has opened up a rich pool of uncharacterized metabolic pathways, enzymes, and adaptations. This great untapped pool of genes provides the particularly exciting potential to mine for new biochemical activities or novel enzymes with activities tailored to peculiar sets of environmental conditions. Metagenomes also represent a huge reservoir of novel enzymes for applications in biocatalysis, biofuels, and bioremediation. Here we present the results of enzyme discovery for four enzyme activities, of particular industrial or environmental interest, including esterase/lipase, glycosyl hydrolase, protease and dehalogenase.

  20. Fungal Strains as Catalysts for the Biotransformation of Halolactones by Hydrolytic Dehalogenation with the Dimethylcyclohexane System

    Directory of Open Access Journals (Sweden)

    Małgorzata Grabarczyk

    2012-08-01

    Full Text Available Bicyclic chloro-, bromo- and iodo-γ-lactones with dimethylcyclohexane rings were used as substrates for bioconversion by several fungal strains (Fusarium, Botrytis and Beauveria. Most of the selected microorganisms transformed these lactones by hydrolytic dehalogenation into the new compound cis-2-hydroxy-4,6-dimethyl-9-oxabicyclo[4.3.0]- nonan-8-one, mainly the (−-isomer. When iodo-γ-lactone was used as the substrate, two products were observed: a hydroxy-γ-lactone and an unsaturated lactone. The structures of all substrates and products were established on the basis of their spectral data. The mechanism of dehalogenation of three halolactones was also studied.

  1. Effect of peat extract on the hydrolytic enzymes of Phanerochaete chrysosporium

    Energy Technology Data Exchange (ETDEWEB)

    Nawaz, M; Gunasekaran, M

    1988-08-01

    Peat, a partially decomposed plant material rich in minerals and lignocellulose was tested as a substrate for the growth and production of hydrolytic enzymes viz. cellulase, cellobiase and xylanase in Phanerochaete chrysosporium. Three types of peat extracts such as cold, hot water and autoclaved were prepared and tested. Among them, autoclaved extract supported the maximal growth. The intracellular enzyme activities peaked on the fifth day after inoculation irrespective of the media and enzyme tested. Addition of cellobiose and lactose in the medium induced the production of cellulase, xylanase and to a lesser extent cellobiase. Addition of glucose and sucrose to the media resulted in the suppression of all the extracellular enzymes tested. 18 refs., 5 figs.

  2. Hydrolytically stable fluorinated metal-organic frameworks for energy-efficient dehydration

    KAUST Repository

    Cadiau, Amandine

    2017-05-18

    Natural gas must be dehydrated before it can be transported and used, but conventional drying agents such as activated alumina or inorganic molecular sieves require an energy-intensive desiccant-regeneration step. We report a hydrolytically stable fluorinated metal-organic framework, AlFFIVE-1-Ni (KAUST-8), with a periodic array of open metal coordination sites and fluorine moieties within the contracted square-shaped one-dimensional channel. This material selectively removed water vapor from gas streams containing CO2, N2, CH4, and higher hydrocarbons typical of natural gas, as well as selectively removed both H2O and CO2 in N2-containing streams. The complete desorption of the adsorbed water molecules contained by the AlFFIVE-1-Ni sorbent requires relatively moderate temperature (~105°C) and about half the energy input for commonly used desiccants.

  3. Identification of thermophilic bacterial strains producing thermotolerant hydrolytic enzymes from manure compost.

    Science.gov (United States)

    Charbonneau, David M; Meddeb-Mouelhi, Fatma; Boissinot, Maurice; Sirois, Marc; Beauregard, Marc

    2012-03-01

    Ten thermophilic bacterial strains were isolated from manure compost. Phylogenetic analysis based on 16S rRNA genes and biochemical characterization allowed identification of four different species belonging to four genera: Geobacillus thermodenitrificans, Bacillus smithii, Ureibacillus suwonensis and Aneurinibacillus thermoaerophilus. PCR-RFLP profiles of the 16S-ITS-23S rRNA region allowed us to distinguish two subgroups among the G. thermodenitrificans isolates. Isolates were screened for thermotolerant hydrolytic activities (60-65°C). Thermotolerant lipolytic activities were detected for G. thermodenitrificans, A. thermoaerophilus and B. smithii. Thermotolerant protease, α-amylase and xylanase activities were also observed in the G. thermodenitrificans group. These species represent a source of potential novel thermostable enzymes for industrial applications.

  4. Biogas production from brewery spent grain enhanced by bioaugmentation with hydrolytic anaerobic bacteria.

    Science.gov (United States)

    Čater, Maša; Fanedl, Lijana; Malovrh, Špela; Marinšek Logar, Romana

    2015-06-01

    Lignocellulosic substrates are widely available but not easily applied in biogas production due to their poor anaerobic degradation. The effect of bioaugmentation by anaerobic hydrolytic bacteria on biogas production was determined by the biochemical methane potential assay. Microbial biomass from full scale upflow anaerobic sludge blanket reactor treating brewery wastewater was a source of active microorganisms and brewery spent grain a model lignocellulosic substrate. Ruminococcus flavefaciens 007C, Pseudobutyrivibrio xylanivorans Mz5(T), Fibrobacter succinogenes S85 and Clostridium cellulovorans as pure and mixed cultures were used to enhance the lignocellulose degradation and elevate the biogas production. P. xylanivorans Mz5(T) was the most successful in elevating methane production (+17.8%), followed by the coculture of P. xylanivorans Mz5(T) and F. succinogenes S85 (+6.9%) and the coculture of C. cellulovorans and F. succinogenes S85 (+4.9%). Changes in microbial community structure were detected by fingerprinting techniques. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Mechanical properties, morphology, and hydrolytic degradation behavior of polylactic acid / natural rubber blends

    Science.gov (United States)

    Buys, Y. F.; Aznan, A. N. A.; Anuar, H.

    2018-01-01

    Due to its biodegradability and renewability, polylactic acid (PLA) has been receiving enormous attention as a potential candidate to replace petroleum based polymers. However, PLA has limitation due to its inherent brittleness. In order to overcome this limitation, blending PLA with elastomeric materials such as natural rubber (NR) are commonly reported. In previous, several researches on PLA/NR blend had been reported, with most of them evaluated the mechanical properties. On the other hand, study of degradation behavior is significance of importance, as controlling materials degradation is required in some applications. This research studied the effect of blend composition on mechanical properties, morphology development, and hydrolytic degradation behavior of PLA/NR blends. Various compositions of PLA/NR blends were prepared by melt blending technique. Tensile test and impact test of the blends were performed to evaluate the mechanical properties. Addition of NR improved the elongation at break and impact strength of the blends, but reduced the tensile strength and stiffness of the specimens. Dynamic Mechanical Analysis (DMA) measurements of the blends displayed two peaks at temperature -70˚C which corresponded to T g of NR and 65˚C which corresponded to T g of PLA. Field Emission Scanning Electron Microscopy (FE-SEM) micrograph of 70/30 PLA/NR specimen also showed two distinct phases, which lead to indication that PLA/NR blends are immiscible. Hydrolytic degradation behavior was evaluated by measuring the remaining weight of the samples immersed in sodium hydroxide solution for a predetermined times. It was shown that the degradation behavior of PLA/NR blends is affected by composition of the blends, with 100 PLA and 70/30 PLA/NR blend showed the fastest degradation rate and 100 NR displayed the slowest one.

  6. Variation in pH optima of hydrolytic enzyme activities in tropical rain forest soils.

    Science.gov (United States)

    Turner, Benjamin L

    2010-10-01

    Extracellular enzymes synthesized by soil microbes play a central role in the biogeochemical cycling of nutrients in the environment. The pH optima of eight hydrolytic enzymes involved in the cycles of carbon, nitrogen, phosphorus, and sulfur, were assessed in a series of tropical forest soils of contrasting pH values from the Republic of Panama. Assays were conducted using 4-methylumbelliferone-linked fluorogenic substrates in modified universal buffer. Optimum pH values differed markedly among enzymes and soils. Enzymes were grouped into three classes based on their pH optima: (i) enzymes with acidic pH optima that were consistent among soils (cellobiohydrolase, β-xylanase, and arylsulfatase), (ii) enzymes with acidic pH optima that varied systematically with soil pH, with the most acidic pH optima in the most acidic soils (α-glucosidase, β-glucosidase, and N-acetyl-β-glucosaminidase), and (iii) enzymes with an optimum pH in either the acid range or the alkaline range depending on soil pH (phosphomonoesterase and phosphodiesterase). The optimum pH values of phosphomonoesterase were consistent among soils, being 4 to 5 for acid phosphomonoesterase and 10 to 11 for alkaline phosphomonoesterase. In contrast, the optimum pH for phosphodiesterase activity varied systematically with soil pH, with the most acidic pH optima (3.0) in the most acidic soils and the most alkaline pH optima (pH 10) in near-neutral soils. Arylsulfatase activity had a very acidic optimum pH in all soils (pH ≤3.0) irrespective of soil pH. The differences in pH optima may be linked to the origins of the enzymes and/or the degree of stabilization on solid surfaces. The results have important implications for the interpretation of hydrolytic enzyme assays using fluorogenic substrates.

  7. Enzymatic Kinetic Resolution of Silybin Diastereoisomers

    Czech Academy of Sciences Publication Activity Database

    Monti, D.; Gažák, Radek; Marhol, Petr; Biedermann, David; Purchartová, Kateřina; Fedrigo, M.; Riva, S.; Křen, Vladimír

    2010-01-01

    Roč. 73, č. 4 (2010), s. 613-619 ISSN 0163-3864 R&D Projects: GA ČR GAP207/10/0288; GA MŠk(CZ) LC06010; GA MŠk OC08049 Institutional research plan: CEZ:AV0Z50200510 Keywords : MARIANUM MILK THISTLE * PROSTATE-CANCER * SILYMARIN Subject RIV: CC - Organic Chemistry Impact factor: 2.872, year: 2010

  8. The effect of the source of microorganisms on adaptation of hydrolytic consortia dedicated to anaerobic digestion of maize silage.

    Science.gov (United States)

    Poszytek, Krzysztof; Pyzik, Adam; Sobczak, Adam; Lipinski, Leszek; Sklodowska, Aleksandra; Drewniak, Lukasz

    2017-08-01

    The main aim of this study was to evaluate the effect of the source of microorganisms on the selection of hydrolytic consortia dedicated to anaerobic digestion of maize silage. The selection process was investigated based on the analysis of changes in the hydrolytic activity and the diversity of microbial communities derived from (i) a hydrolyzer of a commercial agricultural biogas plant, (ii) cattle slurry and (iii) raw sewage sludge, during a series of 10 passages. Following the selection process, the adapted consortia were thoroughly analyzed for their ability to utilize maize silage and augmentation of anaerobic digestion communities. The results of selection of the consortia showed that every subsequent passage of each consortium leads to their adaptation to degradation of maize silage, which was manifested by the increased hydrolytic activity of the adapted consortia. Biodiversity analysis (based on the 16S rDNA amplicon sequencing) confirmed the changes microbial community of each consortium, and showed that after the last (10th) passage all microbial communities were dominated by the representatives of Lactobacillaceae, Prevotellaceae, Veillonellaceae. The results of the functional analyses showed that the adapted consortia improved the efficiency of maize silage degradation, as indicated by the increase in the concentration of glucose and volatile fatty acids (VFAs), as well as the soluble chemical oxygen demand (sCOD). Moreover, bioaugmentation of anaerobic digestion communities by the adapted hydrolytic consortia increased biogas yield by 10-29%, depending on the origin of the community. The obtained results also indicate that substrate input (not community origin) was the driving force responsible for the changes in the community structure of hydrolytic consortia dedicated to anaerobic digestion. Copyright © 2017 Elsevier Ltd. All rights reserved.

  9. Kinetic Interface

    DEFF Research Database (Denmark)

    2009-01-01

    A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises.......A kinetic interface for orientation detection in a video training system is disclosed. The interface includes a balance platform instrumented with inertial motion sensors. The interface engages a participant's sense of balance in training exercises....

  10. Preparation of hydrolytic liquid from dried distiller's grains with solubles and fumaric acid fermentation by Rhizopus arrhizus RH 7-13.

    Science.gov (United States)

    Liu, Huan; Yue, Xuemin; Jin, Yuhan; Wang, Meng; Deng, Li; Wang, Fang; Tan, Tianwei

    2017-10-01

    Fumaric acid production from lignocellulosic materials is an alternative chemicals production system. This work investigated the suitable conditions for hydrolysis of dried distiller's grains with solubles (DDGS). The hydrolytic liquid was subsequently used for the production of fumaric acid. After optimizing the hydrolysis conditions, the most suitable concentration of H 2 SO 4 (2%), hydrolysis temperature (120 °C), hydrolysis time (100min) and solid/liquid ratio (1:10) were obtained. The yield of monosaccharides reached 258 mg/g DDGS and 15.88 g/L glucose, 7.53 g/L xylose and 2.35 g/L arabinose were obtained in unprocessed hydrolytic liquid. The furfural inhibitor in the hydrolytic liquid was also detected and the yield of it was reducing progressively in the pretreatment process. The ferment ability of the hydrolytic liquid from DDGS was tested through the process of fumaric acid production by Rhizopus arrhizus RH 7-13. The unprocessed hydrolytic liquid was not appropriate for the fermentation process. The yield of fumaric acid from the concentrated processed hydrolytic liquid reached 18.93 g/L, which was close to the yield of fermenting 80 g/L glucose. This result indicated that the commonly used carbon resource glucose could to some extent be replaced by processed hydrolytic liquid. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Kinetics and

    Directory of Open Access Journals (Sweden)

    Mojtaba Ahmadi

    2016-11-01

    Full Text Available The aqueous degradation of Reactive Yellow 84 (RY84 by potassium peroxydisulfate (K2S2O8 has been studied in laboratory scale experiments. The effect of the initial concentrations of potassium peroxydisulfate and RY84, pH and temperature on RY84 degradation were also examined. Experimental data were analyzed using first and second-order kinetics. The degradation kinetics of RY84 of the potassium peroxydisulfate process followed the second-order reaction kinetics. These rate constants have an extreme values similar to of 9.493 mM−1min−1 at a peroxydisulfate dose of 4 mmol/L. Thermodynamic parameters such as activation (Ea and Gibbs free energy (ΔG° were also evaluated. The negative value of ΔGo and Ea shows the spontaneous reaction natural conditions and exothermic nature.

  12. Granulocyte kinetics

    International Nuclear Information System (INIS)

    Peters, A.M.; Lavender, J.P.; Saverymuttu, S.H.

    1985-01-01

    By using density gradient materials enriched with autologous plasma, the authors have been able to isolate granulocutes from other cellular elements and label them with In-111 without separation from a plasma environment. The kinetic behavior of these cells suggests that phenomena attributed to granulocyte activation are greatly reduced by this labeling. Here, they review their study of granulocyte kinetics in health and disease in hope of quantifying sites of margination and identifying principal sites of destruction. The three principle headings of the paper are distribution, life-span, and destruction

  13. On the chemical resolution of the {sup 87}Rb{sup +} (s{sup 0})/{sup 87}Sr{sup +} (s{sup 1}) isobaric interference: A kinetic search for an optimum reagent

    Energy Technology Data Exchange (ETDEWEB)

    Cheng Ping; Koyanagi, Gregory K. [Department of Chemistry, Centre for Research in Mass Spectrometry and Centre for Research in Earth and Space Science, York University, Toronto, Ontario, M3J 1P3 (Canada); Bohme, Diethard K. [Department of Chemistry, Centre for Research in Mass Spectrometry and Centre for Research in Earth and Space Science, York University, Toronto, Ontario, M3J 1P3 (Canada)], E-mail: dkbohme@yorku.ca

    2008-10-03

    Room-temperature reactions of the atomic cations Sr{sup +} and Rb{sup +} have been surveyed systematically with a variety of gases using an Inductively-Coupled Plasma/Selected-Ion Flow Tube (ICP/SIFT) tandem mass spectrometer. Rate coefficients and product distributions have been measured in He buffer gas at 0.35 Torr and 295 K for reactions of Sr{sup +} and Rb{sup +} with CH{sub 3}F, CH{sub 3}Cl, N{sub 2}O, CO{sub 2}, CS{sub 2}, SF{sub 6}, D{sub 2}O and NH{sub 3}. Rb{sup +} (s{sup 0}) is seen to be quite inert with these molecules and reacts either slowly by molecule addition or not at all, while Sr{sup +} (s{sup 1}) is much more reactive with all these 8 molecules, especially with CH{sub 3}F, CH{sub 3}Cl, N{sub 2}O and SF{sub 6}. Sr{sup +} reacts with CH{sub 3}F and SF{sub 6} by F-atom transfer, with CH{sub 3}Cl by Cl-atom transfer and with N{sub 2}O by O-atom transfer, and the reaction rate coefficients are all quite high, k {>=} 1.4 x 10{sup -11} cm{sup 3} molecules{sup -1} s{sup -1}. The extreme differences in reactivity with CH{sub 3}F, SF{sub 6}, CH{sub 3}Cl and N{sub 2}O provide a chemical basis for the separation of isobaric interferences of {sup 87}Rb{sup +} and {sup 87}Sr{sup +} often encountered in ICP-MS. Among these four molecules, SF{sub 6} exhibits the largest difference in reactivity, almost a factor of 10{sup 4}, and so is identified as the kinetically recommended reagent for the chemical resolution of the isobaric interference of {sup 87}Rb{sup +} and {sup 87}Sr{sup +}.

  14. Poly[(ethylene oxide)-co-(methylene ethylene oxide)]: A hydrolytically-degradable poly(ethylene oxide) platform.

    Science.gov (United States)

    Lundberg, Pontus; Lee, Bongjae F; van den Berg, Sebastiaan A; Pressly, Eric D; Lee, Annabelle; Hawker, Craig J; Lynd, Nathaniel A

    2012-11-20

    A facile method for imparting hydrolytic degradability to poly(ethylene oxide) (PEO), compatible with current PEGylation strategies, is presented. By incorporating methylene ethylene oxide (MEO) units into the parent PEO backbone, complete degradation was defined by the molar incorporation of MEO, and the structure of the degradation byproducts was consistent with an acid-catalyzed vinyl-ether hydrolysis mechanism. The hydrolytic degradation of poly[(ethylene oxide)-co-(methylene ethylene oxide)] was pH-sensitive, with degradation at pH 5 being significantly faster than at pH 7.4 at 37 °C in PBS buffer while long-term stability could be obtained in either the solid-state or at pH 7.4 at 6 °C.

  15. Biochar amendment to lead-contaminated soil: Effects on fluorescein diacetate hydrolytic activity and phytotoxicity to rice.

    Science.gov (United States)

    Tan, Xiaofei; Liu, Yunguo; Gu, Yanling; Zeng, Guangming; Hu, Xinjiang; Wang, Xin; Hu, Xi; Guo, Yiming; Zeng, Xiaoxia; Sun, Zhichao

    2015-09-01

    The amendment effects of biochar on total microbial activity was measured by fluorescein diacetate (FDA) hydrolytic activity, and phytotoxicity in Pb(II)-contaminated soils was examined by the application of 4 different biochars to soil, with rice as a test plant. The FDA hydrolytic activities of biochar-amended soils were much higher than that of the control. The survival rate of rice in lead-contaminated biochar-amended soils showed significant improvement over the control, especially for bamboo biochar-amended soil (93.3%). In addition, rice grown in lead-contaminated control sediment displayed lower biomass production than that in biochar-amended soil. The immobilization of Pb(II) and the positive effects of biochar amendment on soil microorganisms may account for these effects. The results suggest that biochar may have an excellent ability to mitigate the toxic effects of Pb(II) on soil microorganisms and rice. © 2015 SETAC.

  16. Ultrasound-assisted extraction and characterization of hydrolytic and oxidative enzymes produced by solid state fermentation.

    Science.gov (United States)

    Szabo, Orsolya Erzsebet; Csiszar, Emilia; Toth, Karolina; Szakacs, George; Koczka, Bela

    2015-01-01

    Ligninolytic and hydrolytic enzymes were produced with six selected fungi on flax substrate by solid state fermentation (SSF). The extracellular enzyme production of the organisms in two SSF media was evaluated by measuring the soluble protein concentration and the filter paper, endoxylanase, 1,4-β-d-glucosidase, 1,4-β-d-endoglucanase, polygalacturonase, lignin peroxidase, manganese peroxidase and laccase activities of the clear culture solutions produced by conventional extraction from the SSF materials. The SSF material of the best enzyme producer (Trichoderma virens TUB F-498) was further investigated to enhance the enzyme recovery by low frequency ultrasound treatment. Performance of both the original and ultrasound macerated crude enzyme mixtures was evaluated in degradation of the colored lignin-containing and waxy materials of raw linen fabric. Results proved that sonication (at 40%, 60% and 80% amplitudes, for 60min) did not result in reduction in the filter paper, lignin peroxidase and laccase activities of the crude enzyme solution, but has a significant positive effect on the efficiency of enzyme extraction from the SSF material. Depending on the parameters of sonication, the enzyme activities in the extracts obtained can be increased up to 129-413% of the original activities measured in the control extracts recovered by a common magnetic stirrer. Sonication also has an effect on both the enzymatic removal of the lignin-containing color materials and hydrophobic surface layer from the raw linen. Copyright © 2014 Elsevier B.V. All rights reserved.

  17. Lignocellulosic Fermentation of Wild Grass Employing Recombinant Hydrolytic Enzymes and Fermentative Microbes with Effective Bioethanol Recovery

    Directory of Open Access Journals (Sweden)

    Saprativ P. Das

    2013-01-01

    Full Text Available Simultaneous saccharification and fermentation (SSF studies of steam exploded and alkali pretreated different leafy biomass were accomplished by recombinant Clostridium thermocellum hydrolytic enzymes and fermentative microbes for bioethanol production. The recombinant C. thermocellum GH5 cellulase and GH43 hemicellulase genes expressed in Escherichia coli cells were grown in repetitive batch mode, with the aim of enhancing the cell biomass production and enzyme activity. In batch mode, the cell biomass (A600 nm of E. coli cells and enzyme activities of GH5 cellulase and GH43 hemicellulase were 1.4 and 1.6 with 2.8 and 2.2 U·mg−1, which were augmented to 2.8 and 2.9 with 5.6 and 3.8 U·mg−1 in repetitive batch mode, respectively. Steam exploded wild grass (Achnatherum hymenoides provided the best ethanol titres as compared to other biomasses. Mixed enzyme (GH5 cellulase, GH43 hemicellulase mixed culture (Saccharomyces cerevisiae, Candida shehatae system gave 2-fold higher ethanol titre than single enzyme (GH5 cellulase single culture (Saccharomyces cerevisiae system employing 1% (w/v pretreated substrate. 5% (w/v substrate gave 11.2 g·L−1 of ethanol at shake flask level which on scaling up to 2 L bioreactor resulted in 23 g·L−1 ethanol. 91.6% (v/v ethanol was recovered by rotary evaporator with 21.2% purification efficiency.

  18. A novel hydrolytic product from flesh of Mactra veneriformis and its bioactivities in calcium supplement

    Science.gov (United States)

    Wang, Lingchong; Chen, Shiyong; Liu, Rui; Wu, Hao

    2012-09-01

    To prepare calcium-binding peptides, the flesh residue of Mactra Veneriformis was subjected to enzymatic hydrolysis. By comparing the capability of combining calcium of the hydrolyzates, pepsin was confirmed to be the most suitable enzyme for hydrolyzing the flesh residue to release calcium-binding peptides among the seven tested proteases. The pepsin hydrolyzate (PHM) was divided into three fractions according to the molecule weight of its composition, which ranged from 0.5 to 15 kDa. The low-molecule-weight fraction named PHM-3 had the highest capability in combining calcium. The peptides existing in the PHM-3 fraction consisted of higher contents of Glu, Ala and Leu, and could produce one type of calcium-peptide complex by powerfully chelating calcium ions. PHM-3 products could effectively increase calcium absorption and retention while they decreased the calcium excretion in animal tests. Additionally, symptoms caused by low calcium bioavailability in ovariectomized rats, such as bone mineral density reduction and mechanical strength loss could be significantly ameliorated by the hydrolytic products addition in diet.

  19. Quantitative iTRAQ secretome analysis of Aspergillus niger reveals novel hydrolytic enzymes.

    Science.gov (United States)

    Adav, Sunil S; Li, An A; Manavalan, Arulmani; Punt, Peter; Sze, Siu Kwan

    2010-08-06

    The natural lifestyle of Aspergillus niger made them more effective secretors of hydrolytic proteins and becomes critical when this species were exploited as hosts for the commercial secretion of heterologous proteins. The protein secretion profile of A. niger and its mutant at different pH was explored using iTRAQ-based quantitative proteomics approach coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS). This study characterized 102 highly confident unique proteins in the secretome with zero false discovery rate based on decoy strategy. The iTRAQ technique identified and relatively quantified many hydrolyzing enzymes such as cellulases, hemicellulases, glycoside hydrolases, proteases, peroxidases, and protein translocating transporter proteins during fermentation. The enzymes have potential application in lignocellulosic biomass hydrolysis for biofuel production, for example, the cellulolytic and hemicellulolytic enzymes glucan 1,4-alpha-glucosidase, alpha-glucosidase C, endoglucanase, alpha l-arabinofuranosidase, beta-mannosidase, glycosyl hydrolase; proteases such as tripeptidyl-peptidase, aspergillopepsin, and other enzymes including cytochrome c oxidase, cytochrome c oxidase, glucose oxidase were highly expressed in A. niger and its mutant secretion. In addition, specific enzyme production can be stimulated by controlling pH of the culture medium. Our results showed comprehensive unique secretory protein profile of A. niger, its regulation at different pH, and the potential application of iTRAQ-based quantitative proteomics for the microbial secretome analysis.

  20. Stimulation of the hydrolytic stage for biogas production from cattle manure in an electrochemical bioreactor.

    Science.gov (United States)

    Samani, Saeed; Abdoli, Mohammad Ali; Karbassi, Abdolreza; Amin, Mohammad Mehdi

    Electrical current in the hydrolytic phase of the biogas process might affect biogas yield. In this study, four 1,150 mL single membrane-less chamber electrochemical bioreactors, containing two parallel titanium plates were connected to the electrical source with voltages of 0, -0.5, -1 and -1.5 V, respectively. Reactor 1 with 0 V was considered as a control reactor. The trend of biogas production was precisely checked against pH, oxidation reduction potential and electrical power at a temperature of 37 ± 0.5°C amid cattle manure as substrate for 120 days. Biogas production increased by voltage applied to Reactors 2 and 3 when compared with the control reactor. In addition, the electricity in Reactors 2 and 3 caused more biogas production than Reactor 4. Acetogenic phase occurred more quickly in Reactor 3 than in the other reactors. The obtained results from Reactor 4 were indicative of acidogenic domination and its continuous behavior under electrical stimulation. The results of the present investigation clearly revealed that phasic electrical current could enhance the efficiency of biogas production.

  1. Hydrolytic enzyme activities in shiitake mushroom (Lentinula edodes) strains cultivated on coffee pulp.

    Science.gov (United States)

    Mata, Gerardo; Salmones, Dulce; Pérez-Merlo, Rosalía

    Hydrolytic enzyme production (cellulases, laminarinases and xylanases) was studied in cultures of Lentinula edodes on sterilized coffee pulp. Samples of substrate colonized by mycelia were taken after 7, 14, 21, 28 and 35 days of incubation at 25°C (W1 to W5) and during the fruiting period at different stages: formation of primordia (PF), first harvest (H) and one week after the first harvest (PH). The enzymatic activity was lower during the early mycelial growth and showed higher levels during the formation and development of fruiting bodies. During the reproductive stage of the fungus, the samples were subjected to a soaking treatment; however, it was not possible to relate this soaking treatment to the increase in enzyme production. The levels of enzymatic activity suggest that secretion of the studied enzymes does not influence the adaptability of the strains to the substrate. Copyright © 2016 Asociación Argentina de Microbiología. Publicado por Elsevier España, S.L.U. All rights reserved.

  2. Hydrolytic and thermal degradation of PCL and PCL/Bentonite compounds

    Energy Technology Data Exchange (ETDEWEB)

    Franca, Danyelle Campos; Bezerra, Elieber Barros; Morais, Dayanne Diniz de Souza; Araujo, Edcleide Maria [Universidade Federal de Campina grande (UFCG), PB (Brazil). Departamento de Engenharia de Materiais; Wellen, Renate Maria Ramos, E-mail: wellen.renate@gmail.com [Universidade Federal da Paraiba (UFPB), Joao Pessoa, PB (Brazil). Departamento de Engenharia de Materiais

    2016-05-15

    Poly(ε-caprolactone)/montmorillonite (PCL/MMT) and Poly(εcaprolactone)/organo-modified montmorillonite (PCL/OMMT) compounds at 3% w/w clay content were prepared by melting mixing. The effect of MMT and OMMT on the degradability of PCL injected specimens was investigated in vacuum at 40 deg C for up to 45 days and in aqueous medium at 40 deg C for up to 45 days. Selected specimens were collected after 15, 30 and 45 days of exposure. Microstructural changes were monitored during the degradation experiment by means of melt flow rate (MFR), weight loss, X ray diffraction (XRD), mechanical properties, and scanning electron microscopy (SEM). PCL and its compounds revealed not to be prone to hydrolytic degradation with similar results for MFR of samples exposed in vacuum and water. Gain and loss of weight were observed during experiments, probably due to swelling mechanism taking place in two stages, with the amorphous phase being the first to be swelled followed by the crystalline one. By XRD a new peak corresponding to (002) plane was evident for PCL/OMMT. PCL proved to be resistant to degradation since experiments carried out in vacuum or in aqueous medium for up to 45 days were not enough to affect the mechanical integrity of PCL samples. (author)

  3. Role of carbon source in the shift from oxidative to hydrolytic wood decomposition by Postia placenta.

    Science.gov (United States)

    Zhang, Jiwei; Schilling, Jonathan S

    2017-09-01

    Brown rot fungi initiate wood decay using oxidative pretreatments to improve access for cellulolytic enzymes. These pretreatments are incompatible with enzymes, and we recently showed that Postia placenta overcomes this issue by delaying glycoside hydrolase (GH) gene upregulation briefly (wood wafers and spatially mapped expression (via quantitative PCR) of twelve ORs and GHs targeted using functional genomics analyses. By layering expression patterns over solubilized sugar data (via HPLC) from wood, we observed solubilization of wood glucose, cellobiose, mannose, and xylose coincident with the OR-GH transition. We then tested effects of these soluble sugars, plus polymeric carbon sources (spruce powder, cellulose), on P. placenta gene expression in liquid cultures. Expression of ORs was strictly (aox1, cro5) or progressively repressed over time (qrd1, lcc1) by all soluble sugars, including cellobiose, but not by polymeric sources. Simple sugars repressed hemicellulase gene expression over time, but these sugars did not repress cellulases. Cellulase genes were upregulated, however, along with hemicellulases in the presence of soluble cellobiose and in the presence of polymeric carbon sources, relative to starvation (carbon-free). This verifies an inducible cellulase system in P. placenta that lacks carbon catabolite repression (CCR), and it suggests that brown rot fungi use soluble sugars, particularly cellobiose, to cue a critical oxidative-hydrolytic transition. Copyright © 2017 Elsevier Inc. All rights reserved.

  4. Ultra-Small Fatty Acid-Stabilized Magnetite Nanocolloids Synthesized by In Situ Hydrolytic Precipitation

    Directory of Open Access Journals (Sweden)

    Kheireddine El-Boubbou

    2015-01-01

    Full Text Available Simple, fast, large-scale, and cost-effective preparation of uniform controlled magnetic nanoparticles remains a major hurdle on the way towards magnetically targeted applications at realistic technical conditions. Herein, we present a unique one-pot approach that relies on simple basic hydrolytic in situ coprecipitation of inexpensive metal salts (Fe2+ and Fe3+ compartmentalized by stabilizing fatty acids and aided by the presence of alkylamines. The synthesis was performed at relatively low temperatures (~80°C without the use of high-boiling point solvents and elevated temperatures. This method allowed for the production of ultra-small, colloidal, and hydrophobically stabilized magnetite metal oxide nanoparticles readily dispersed in organic solvents. The results reveal that the obtained magnetite nanoparticles exhibit narrow size distributions, good monodispersities, high saturation magnetizations, and excellent colloidal stabilities. When the [fatty acid] : [Fe] ratio was varied, control over nanoparticle diameters within the range of 2–10 nm was achieved. The amount of fatty acid and alkylamine used during the reaction proved critical in governing morphology, dispersity, uniformity, and colloidal stability. Upon exchange with water-soluble polymers, the ultra-small sized particles become biologically relevant, with great promise for theranostic applications as imaging and magnetically targeted delivery vehicles.

  5. Hydrolytic and thermal degradation of PCL and PCL/Bentonite compounds

    International Nuclear Information System (INIS)

    Franca, Danyelle Campos; Bezerra, Elieber Barros; Morais, Dayanne Diniz de Souza; Araujo, Edcleide Maria; Wellen, Renate Maria Ramos

    2016-01-01

    Poly(ε-caprolactone)/montmorillonite (PCL/MMT) and Poly(εcaprolactone)/organo-modified montmorillonite (PCL/OMMT) compounds at 3% w/w clay content were prepared by melting mixing. The effect of MMT and OMMT on the degradability of PCL injected specimens was investigated in vacuum at 40 deg C for up to 45 days and in aqueous medium at 40 deg C for up to 45 days. Selected specimens were collected after 15, 30 and 45 days of exposure. Microstructural changes were monitored during the degradation experiment by means of melt flow rate (MFR), weight loss, X ray diffraction (XRD), mechanical properties, and scanning electron microscopy (SEM). PCL and its compounds revealed not to be prone to hydrolytic degradation with similar results for MFR of samples exposed in vacuum and water. Gain and loss of weight were observed during experiments, probably due to swelling mechanism taking place in two stages, with the amorphous phase being the first to be swelled followed by the crystalline one. By XRD a new peak corresponding to (002) plane was evident for PCL/OMMT. PCL proved to be resistant to degradation since experiments carried out in vacuum or in aqueous medium for up to 45 days were not enough to affect the mechanical integrity of PCL samples. (author)

  6. Inhibitors of the Hydrolytic Enzyme Dimethylarginine Dimethylaminohydrolase (DDAH: Discovery, Synthesis and Development

    Directory of Open Access Journals (Sweden)

    Rhys B. Murphy

    2016-05-01

    Full Text Available Dimethylarginine dimethylaminohydrolase (DDAH is a highly conserved hydrolytic enzyme found in numerous species, including bacteria, rodents, and humans. In humans, the DDAH-1 isoform is known to metabolize endogenous asymmetric dimethylarginine (ADMA and monomethyl arginine (l-NMMA, with ADMA proposed to be a putative marker of cardiovascular disease. Current literature reports identify the DDAH family of enzymes as a potential therapeutic target in the regulation of nitric oxide (NO production, mediated via its biochemical interaction with the nitric oxide synthase (NOS family of enzymes. Increased DDAH expression and NO production have been linked to multiple pathological conditions, specifically, cancer, neurodegenerative disorders, and septic shock. As such, the discovery, chemical synthesis, and development of DDAH inhibitors as potential drug candidates represent a growing field of interest. This review article summarizes the current knowledge on DDAH inhibition and the derived pharmacokinetic parameters of the main DDAH inhibitors reported in the literature. Furthermore, current methods of development and chemical synthetic pathways are discussed.

  7. THE COORDINATION COMPOUNDS OF COBALT (II, III) WITH DITHIOCARBAMIC ACID DERIVATIVES — MODIFICATORS OF HYDROLYTIC ENZYMES ACTIVITY

    OpenAIRE

    L. D. Varbanets; О. V. Matselyukh; N. А. Nidyalkova; Е. V. Аvdiyuk; А. V. Gudzenko; I. I. Seifullina; G. N. Маsаnоvets; N. V. Khitrich

    2013-01-01

    Chloride, bromide and isothiocyanate complexes of cobalt(II) with N-substituted thiocarbamoyl-N?-pentamethylenesulfenamides (1)–(12), and also complexes of cobalt(II, Ш) with derivatives of morpholine-4-carbodithioic acid (13)–(18) have been used as modificators of enzymes of hydrolytic action — Bacillus thurin-giensis ІМВ В-7324 peptidases, Bacillus subtilis 147 and Aspergillus flavus var. oryzae 80428 amylases, Eupenicillium erubescens 248 and Cryptococcus albidus 1001 rhamnosidases. It was...

  8. Unravelling the Interactions between Hydrolytic and Oxidative Enzymes in Degradation of Lignocellulosic Biomass by Sporothrix carnis under Various Fermentation Conditions

    Directory of Open Access Journals (Sweden)

    Olusola A. Ogunyewo

    2016-01-01

    Full Text Available The mechanism underlying the action of lignocellulolytic enzymes in biodegradation of lignocellulosic biomass remains unclear; hence, it is crucial to investigate enzymatic interactions involved in the process. In this study, degradation of corn cob by Sporothrix carnis and involvement of lignocellulolytic enzymes in biodegradation were investigated over 240 h cultivation period. About 60% degradation of corn cob was achieved by S. carnis at the end of fermentation. The yields of hydrolytic enzymes, cellulase and xylanase, were higher than oxidative enzymes, laccase and peroxidase, over 144 h fermentation period. Maximum yields of cellulase (854.4 U/mg and xylanase (789.6 U/mg were at 96 and 144 h, respectively. Laccase and peroxidase were produced cooperatively with maximum yields of 489.06 U/mg and 585.39 U/mg at 144 h. Drastic decline in production of cellulase at 144 h (242.01 U/mg and xylanase at 192 h (192.2 U/mg indicates that they play initial roles in biodegradation of lignocellulosic biomass while laccase and peroxidase play later roles. Optimal degradation of corn cob (76.6% and production of hydrolytic and oxidative enzymes were achieved with 2.5% inoculum at pH 6.0. Results suggest synergy in interactions between the hydrolytic and oxidative enzymes which can be optimized for improved biodegradation.

  9. Determination of the action modes of cellulases from hydrolytic profiles over a time course using fluorescence-assisted carbohydrate electrophoresis.

    Science.gov (United States)

    Zhang, Qing; Zhang, Xiaomei; Wang, Peipei; Li, Dandan; Chen, Guanjun; Gao, Peiji; Wang, Lushan

    2015-03-01

    Fluorescence-assisted carbohydrate electrophoresis (FACE) is a sensitive and simple method for the separation of oligosaccharides. It relies on labeling the reducing ends of oligosaccharides with a fluorophore, followed by PAGE. Concentration changes of oligosaccharides following hydrolysis of a carbohydrate polymer could be quantitatively measured continuously over time using the FACE method. Based on the quantitative analysis, we suggested that FACE was a relatively high-throughput, repeatable, and suitable method for the analysis of the action modes of cellulases. On account of the time courses of their hydrolytic profiles, the apparent processivity was used to show the different action modes of cellulases. Cellulases could be easily differentiated as exoglucanases, β-glucosidases, or endoglucanases. Moreover, endoglucanases from the same glycoside hydrolases family had a variety of apparent processivity, indicating the different modes of action. Endoglucanases with the same binding capacities and hydrolytic activities had similar oligosaccharide profiles, which aided in their classification. The hydrolytic profile of Trichoderma reesei Cel12A, an endoglucanases from T. reesei, contained glucose, cellobiose, and cellotriose, which revealed that it may have a new glucosidase activity, corresponding to that of EC 3.2.1.74. A hydrolysate study of a T. reesei Cel12A-N20A mutant demonstrated that the FACE method was sufficiently sensitive to detect the influence of a single-site mutation on enzymatic activity. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Saccharification and hydrolytic enzyme production of alkali pre-treated wheat bran by Trichoderma virens under solid state fermentation.

    Science.gov (United States)

    El-Shishtawy, Reda M; Mohamed, Saleh A; Asiri, Abdullah M; Gomaa, Abu-Bakr M; Ibrahim, Ibrahim H; Al-Talhi, Hasan A

    2015-05-28

    In continuation of our previously interest in the saccharification of agriculture wastes by Bacillus megatherium in solid state fermentation (SSF), we wish to report an investigation and comparative evaluation among Trichoderma sp. for the saccharification of four alkali-pretreated agricultural residues and production of hydrolytic enzymes, carboxymethyl cellulase (CMCase), filter paperase (FPase), pectinase (PGase) and xylanase (Xylase) in SSF. The optimization of the physiological conditions of production of hydrolytic enzymes and saccharification content from Trichoderma virens using alkali-pretreated wheat bran was the last goal. The physico-chemical parameters of SSF include incubation time, incubation temperature, moisture content of the substrate, incubation pH, supplementation with carbon and nitrogen sources were optimized. Saccharification of different solid state fermentation sources wheat bran, date's seeds, grass and palm leaves, were tested for the production of fermentable sugar by Trichoderma sp. The maximum production of hydrolytic enzymes CMCase, FPase, PGase and Xylase and saccharification content were obtained on wheat bran. Time course, moisture content, optimum temperature, optimum pH, supplementation with carbon and nitrogen sources were optimized to achieve the maximum production of the hydrolytic enzymes, protein and total carbohydrate of T. virens using alkali pre-treated wheat bran. The maximum production of CMCase, FPase, PGase, Xylase, protein and carbohydrate content was recorded at 72 h of incubation, 50-70 % moisture, temperature 25-35 °C and pH 5. The influence of supplementary carbon and nitrogen sources was studied. While lactose and sucrose enhanced the activity of PGase from 79.2 to 582.9 and 632.6 U/g, starch inhibited all other enzymes. This was confirmed by maximum saccharification content. Among the nitrogen sources, yeast extract and urea enhanced the saccharification content and CMCase, PGase and Xylase. The results of

  11. Physisorption kinetics

    CERN Document Server

    Kreuzer, Hans Jürgen

    1986-01-01

    This monograph deals with the kinetics of adsorption and desorption of molecules physisorbed on solid surfaces. Although frequent and detailed reference is made to experiment, it is mainly concerned with the theory of the subject. In this, we have attempted to present a unified picture based on the master equation approach. Physisorption kinetics is by no means a closed and mature subject; rather, in writing this monograph we intended to survey a field very much in flux, to assess its achievements so far, and to give a reasonable basis from which further developments can take off. For this reason we have included many papers in the bibliography that are not referred to in the text but are of relevance to physisorption. To keep this monograph to a reasonable size, and also to allow for some unity in the presentation of the material, we had to omit a number of topics related to physisorption kinetics. We have not covered to any extent the equilibrium properties of physisorbed layers such as structures, phase tr...

  12. Characterization of CTX-M-140, a Variant of CTX-M-14 Extended-Spectrum β-Lactamase with Decreased Cephalosporin Hydrolytic Activity, from Cephalosporin-Resistant Proteus mirabilis.

    Science.gov (United States)

    Tian, Guo-Bao; Jiang, Yi-Qi; Huang, Ying-Min; Qin, Yun; Feng, Lian-Qiang; Zhang, Xue-Fei; Li, Hong-Yu; Zhong, Lan-Lan; Zeng, Kun-Jiao; Patil, Sandip; Xing, Yong; Huang, Xi

    2016-10-01

    CTX-M-140, a novel CTX-M-type extended-spectrum β-lactamase (ESBL), was identified in cephalosporin-resistant clinical isolates of Proteus mirabilis CTX-M-140 contained an alanine-to-threonine substitution at position 109 compared to its putative progenitor, CTX-M-14. When it was expressed in an Escherichia coli isogenic background, CTX-M-140 conferred 4- to 32-fold lower MICs of cephalosporins than those with CTX-M-14, indicating that the phenotype was attributable to this single substitution. For four mutants of CTX-M-14 that were constructed by site-directed mutagenesis (A109E, A109D, A109K, and A109R mutants), MICs of cephalosporins were similar to those for the E. coli host strain, which suggested that the alanine at position 109 was essential for cephalosporin hydrolysis. The kinetic properties of native CTX-M-14 and CTX-M-140 were consistent with the MICs for the E. coli clones. Compared with that of CTX-M-14, a lower hydrolytic activity against cephalosporins was observed for CTX-M-140. blaCTX-M-140 is located on the chromosome as determined by I-CeuI pulsed-field gel electrophoresis (I-CeuI-PFGE) and Southern hybridization. The genetic environment surrounding blaCTX-M-140 is identical to the sequence found in different plasmids with blaCTX-M-9-group genes among the Enterobacteriaceae Genome sequencing and analysis showed that P. mirabilis strains with blaCTX-M-140 have a genome size of ∼4 Mbp, with a GC content of 38.7% and 23 putative antibiotic resistance genes. Our results indicate that alanine at position 109 is critical for the hydrolytic activity of CTX-M-14 against oxyimino-cephalosporins. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  13. Application of soft- and hard-modelling approaches to resolution of kinetics of electron donor-acceptor complex formation of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with imipramine in different solutions

    International Nuclear Information System (INIS)

    Hasani, Masoumeh; Shariati-Rad, Masoud; Abdollahi, Hamid

    2009-01-01

    Kinetics of electron donor-acceptor (EDA) complex formation of imipramine and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) was investigated spectrophotometrically in acetonitrile, 1,2-dichloroethane, and chloroform solutions using soft- and hard-modelling approaches. From the results of exploratory analysis of kinetic data and the spectral changes by soft-modelling approaches, evolving factor analysis (EFA) and orthogonal projection approach (OPA), a consecutive two-steps reaction with two intermediates was proposed for the process in acetonitrile and 1,2-dichloroethane media and one with a single intermediate in chloroform solution. Secondly, by applying, multivariate nonlinear least squares hard-modelling approach on the collected experimental kinetic data matrix, the nonlinear parameters (rate constants) as well as the linear parameters (spectral profiles) were obtained by fitting the collected experimental kinetic data matrix to the proposed model. Small values of standard deviation in the resulting parameters and sum of squares of the residuals (ssq) obtained showed the proper selection of the model. Furthermore, the values of lack of fit and percent of explained variance confirmed the correct identified models. Identification of the model with the aid of soft-modelling approaches followed by application of the hard-modelling approaches decreases significantly the rotational ambiguity associated with the obtained concentration and spectral profiles. Variations in the kinetic constants were in complete agreement with the model proposed and the solvent polarities

  14. Application of soft- and hard-modelling approaches to resolution of kinetics of electron donor-acceptor complex formation of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone with imipramine in different solutions

    Energy Technology Data Exchange (ETDEWEB)

    Hasani, Masoumeh [Faculty of Chemistry, Bu-Ali Sina University, Mahdieh, Hamedan, 65174 (Iran, Islamic Republic of)], E-mail: hasani@basu.ac.ir; Shariati-Rad, Masoud [Faculty of Chemistry, Bu-Ali Sina University, Mahdieh, Hamedan, 65174 (Iran, Islamic Republic of); Abdollahi, Hamid [Department of Chemistry, Institute for Advanced Studies in Basic Sciences, Zanjan (Iran, Islamic Republic of)

    2009-03-23

    Kinetics of electron donor-acceptor (EDA) complex formation of imipramine and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) was investigated spectrophotometrically in acetonitrile, 1,2-dichloroethane, and chloroform solutions using soft- and hard-modelling approaches. From the results of exploratory analysis of kinetic data and the spectral changes by soft-modelling approaches, evolving factor analysis (EFA) and orthogonal projection approach (OPA), a consecutive two-steps reaction with two intermediates was proposed for the process in acetonitrile and 1,2-dichloroethane media and one with a single intermediate in chloroform solution. Secondly, by applying, multivariate nonlinear least squares hard-modelling approach on the collected experimental kinetic data matrix, the nonlinear parameters (rate constants) as well as the linear parameters (spectral profiles) were obtained by fitting the collected experimental kinetic data matrix to the proposed model. Small values of standard deviation in the resulting parameters and sum of squares of the residuals (ssq) obtained showed the proper selection of the model. Furthermore, the values of lack of fit and percent of explained variance confirmed the correct identified models. Identification of the model with the aid of soft-modelling approaches followed by application of the hard-modelling approaches decreases significantly the rotational ambiguity associated with the obtained concentration and spectral profiles. Variations in the kinetic constants were in complete agreement with the model proposed and the solvent polarities.

  15. Non-hydrolytic sol-gel synthesis of epoxysilane-based inorganic-organic hybrid resins

    International Nuclear Information System (INIS)

    Jana, Sunirmal; Lim, Mi Ae; Baek, In Chan; Kim, Chang Hae; Seok, Sang Il

    2008-01-01

    A silica-based inorganic-organic hybrid resins (IOHR) were synthesized by non-hydrolytic sol-gel process from 3-glycidoxypropyltrimethoxysilane (GLYMO) and diphenylsilanediol (DPSD) at a fixed amount of (20 mol%) phenyltrimethoxysilane using barium hydroxide as a catalyst. The confirmation of condensation reaction in the IOHR was done by liquid state 29 Si NMR (Nuclear Magnetic Resonance) spectroscopy, measurement of viscosity as well as weight average molecular weight (W m ) of the IOHR. The W m of the IOHR was varied from 1091 to 2151, depending upon the DPSD content. Fourier transform infrared (FTIR) spectroscopic measurements were performed to investigate the details of vibrational absorption bands in the IOHR. It was seen that up to 50 mol% of DPSD there were no absorption peaks in the region of 3000-3600 cm -1 responsible for O-H groups and it reappeared at 60 mol% of DPSD due to some unreacted OH groups present in the resin. The IOHR at all the compositions was oily transparent liquid, miscible with various organic solvents like toluene, cyclohexanone, chloroform, tehrahydrofuran (THF), etc., and also commercial epoxy resins but immiscible with water. The color of the IOHR was pale yellow, which lightened with increasing DPSD content. The IOHR having 40-50 mol% of DPSD were storable. The refractive index at 632.8 nm of the resin films varied from 1.556 to 1.588, depending upon the resin composition. Physico-chemical properties such as the thermal stability, visible transparency, etc. after curing were investigated as a function of the chemical composition

  16. Yarrowia lipolytica NCIM 3589, a tropical marine yeast, degrades bromoalkanes by an initial hydrolytic dehalogenation step.

    Science.gov (United States)

    Vatsal, Aakanksha; Zinjarde, Smita S; Kumar, Ameeta Ravi

    2015-04-01

    The widespread industrial use of organobromines which are known persistent organic pollutants has led to their accumulation in sediments and water bodies causing harm to animals and humans. While degradation of organochlorines by bacteria is well documented, information regarding degradation pathways of these recalcitrant organobromines is scarce. Hence, their fates and effects on the environment are of concern. The present study shows that a tropical marine yeast, Yarrowia lipolytica NCIM 3589 aerobically degrades bromoalkanes differing in carbon chain length and position of halogen substitution viz., 2-bromopropane (2-BP), 1-bromobutane (1-BB), 1,5 dibromopentane (1,5-DBP) and 1-bromodecane (1-BD) as seen by an increase in cell mass, release of bromide and concomitant decrease in concentration of brominated compound. The amount of bromoalkane degraded was 27.3, 21.9, 18.0 and 38.3 % with degradation rates of 0.076, 0.058, 0.046 and 0.117/day for 2-BP, 1-BB, 1,5-DBP and 1-BD, respectively. The initial product formed respectively were alcohols viz., 2-propanol, 1-butanol, 1-bromo, 5-pentanol and 1-decanol as detected by GC-MS. These were further metabolized to fatty acids viz., 2-propionic, 1-butyric and 1-decanoic acid eventually leading to carbon dioxide formation. Neither higher chain nor brominated fatty acids were detected. An inducible extracellular dehalogenase responsible for removal of bromide was detected with activities of 21.07, 18.82, 18.96 and 26.67 U/ml for 2-BP, 1-BB, 1,5-DBP and 1-BD, respectively. We report here for the first time the proposed aerobic pathway of bromoalkane degradation by an eukaryotic microbe Y. lipolytica 3589, involving an initial hydrolytic dehalogenation step.

  17. The hydrolytic enzymes produced by fungi strains isolated from the sand and soil of recreational areas

    Science.gov (United States)

    Kurnatowski, Piotr; Wójcik, Anna; Błaszkowska, Joanna; Góralska, Katarzyna

    2016-10-01

    The pathogenicity of fungi depends on, inter alia, the secretion of hydrolytic enzymes. The aim of this study was to determine the enzymatic activity of yeasts and yeast-like fungi isolated from children’s recreation areas, and compare the results with literature data of strains obtained from patients with mycoses. The enzymatic activity of 96 strains was assessed using an API ZYM kit (bioMerieux, France) and their biotypes were established. The fungal species were found to produce from 16 to 19 hydrolases: the most active were: leucine arylamidase (e5), acid phosphatase (e10), alkaline phosphatase (e1), naphthol-AS-BI-phosphohydrolase (e11), esterase – C4 (e2), β-galac - tosidase (e13) and β-glucosidase (e16). In addition, 13 biotypes characteristic of particular species of fungi were defined. Most strains could be categorized as biotypes C2 – 39.5% and A – 26%. The examined fungal strains isolated from recreational areas have selected biochemical characteristics i.e. production of hydrolases, which demonstrate their pathogenicity. They produce a number of enzymes which are also present in strains isolated from patients with mycoses, including: leucine arylamidase (e5), acid phosphatase (e10), naphthol-AS-BI-phosphohydrolase (e11) and alkaline phosphatase (e1). The biotypes identified in the course of this study (A, B3, B4, C1, C6 and D3) have been also reported in cases of fungal infection. Therefore, the fungi present in the sand and soil of recreational have pathogenic properties and are possible factors of fungal infection among children.

  18. Rat lingual lipase: partial purification, hydrolytic properties, and comparison with pancreatic lipase.

    Science.gov (United States)

    Roberts, I M; Montgomery, R K; Carey, M C

    1984-10-01

    We have partially purified lingual lipase from the serous glands of rat tongue. With a combination of Triton X-100 extraction or Triton X-114 phase-separation techniques, Bio-Bead SM-2 treatment, dialysis, and gel filtration on Sephadex G-200 or Sephacryl S-300, we obtained a sparingly soluble lipid-free protein demonstrating hydrolytic activity against triglycerides and negligible phospholipase or cholesteryl esterase activities. Compared with homogenate, specific activities of the enzyme were enriched 3- to 5-fold prior to gel filtration and 10-fold after gel filtration. Analysis by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and gel filtration under denaturing conditions (6 M guanidine X HCl or 0.1% sodium dodecyl sulfate) revealed one major glycoprotein band with Mr approximately 50,000. Gel filtration of the active enzyme in 0.1% Triton X-100 gave an Mr approximately 270,000-300,000, suggesting extensive self-aggregation. With both tributyrin and triolein, the pH optimum of the purified enzyme was 4.0 and activity extended from pH 2.0 to 8.0. In contrast to purified human pancreatic lipase, lingual lipase hydrolyzed triglyceride emulsions and mixed micelles stabilized with both short-chain (dihexanoyl) and long-chain (egg) lecithin and were inhibited only slightly (18-25%) by micellar concentrations of two common bile salts, taurodeoxycholate and taurocholate. Our results suggest that the hydrolysis of dietary fat by lingual lipase may extend from the pharynx through the esophagus and stomach and into the upper small intestine.

  19. Immobilization of cholesterol esterase in mesoporous silica materials and its hydrolytic activity toward diethyl phthalate

    Energy Technology Data Exchange (ETDEWEB)

    Orita, Toru, E-mail: nqj45366@nifty.com [Division of Chemistry for Materials, Graduate School of Engineering, Mie University, 1577 Kurimamachiya-cho, Tsu, Mie 514-8570 (Japan); Taiyo Kagaku Co. Ltd., 800 Yamada-cho, Yokkaichi, Mie 512-1111 (Japan); Tomita, Masahiro [Division of Chemistry for Materials, Graduate School of Engineering, Mie University, 1577 Kurimamachiya-cho, Tsu, Mie 514-8570 (Japan); Saito, Takao; Nishida, Nasakazu; Kato, Katsuya [National Institute of Advanced Industrial Science and Technology, 2266-78 Anagahora, Moriyamaku, Nagoya, Aichi 463-8560 (Japan)

    2012-05-01

    Cholesterol esterase (CE, cholesteryl ester hydrolase, EC 3.1.1.13) from porcine pancreas (molecular weight 400-500 kDa) exhibits hydrolytic activity toward various toxic organic phthalate esters. CE was confined in the nanospace (diameter 3-30 nm) of five types of mesoporous silica (MPS) that differ in structural properties such as pore diameter, pore volume, and particle morphology. These structural properties were characterized by transmission electron microscopy, small-angle X-ray diffraction, N{sub 2} adsorption-desorption experiments, solid-state {sup 13}C nuclear magnetic resonance (NMR), and solid-state {sup 29}Si NMR. Catalytic activities of immobilized and free CE were evaluated by the hydrolysis of diethyl phthalate in phosphate buffer solutions containing an organic cosolvent. Optimal activity recovery was achieved when CE was immobilized in n-decane-functionalized MPS, which had a large pore size (22.5 nm). The immobilization also protected against effects of temperature within the range 30 Degree-Sign C-60 Degree-Sign C; CE immobilized in n-decyl-functionalized MPS exhibited better thermal stability than in non-functionalized MPS or free CE. Moreover, it retained approximately 60% of its catalytic activity even after six catalytic cycles. - Highlights: Black-Right-Pointing-Pointer The highest activity of immobilized CE was shown in MPS with a pore size of 22.5 nm. Black-Right-Pointing-Pointer Catalytic efficiency improved when MPS was functionalized by n-decyl substitution. Black-Right-Pointing-Pointer Immobilized CE exhibited good thermal stability and reusability. Black-Right-Pointing-Pointer Organic co-solvent and the substrate structures affected enzyme activities.

  20. Chemical stability of insulin. 1. Hydrolytic degradation during storage of pharmaceutical preparations.

    Science.gov (United States)

    Brange, J; Langkjaer, L; Havelund, S; Vølund, A

    1992-06-01

    Hydrolysis of insulin has been studied during storage of various preparations at different temperatures. Insulin deteriorates rapidly in acid solutions due to extensive deamidation at residue AsnA21. In neutral formulations deamidation takes place at residue AsnB3 at a substantially reduced rate under formation of a mixture of isoAsp and Asp derivatives. The rate of hydrolysis at B3 is independent of the strength of the preparation, and in most cases the species of insulin, but varies with storage temperature and formulation. Total transformation at B3 is considerably reduced when insulin is in the crystalline as compared to the amorphous or soluble state, indicating that formation of the rate-limiting cyclic imide decreases when the flexibility of the tertiary structure is reduced. Neutral solutions containing phenol showed reduced deamidation probably because of a stabilizing effect of phenol on the tertiary structure (alpha-helix formation) around the deamidating residue, resulting in a reduced probability for formation of the intermediate imide. The ratio of isoAsp/Asp derivative was independent of time and temperature, suggesting a pathway involving only intermediate imide formation, without any direct side-chain hydrolysis. However, increasing formation of Asp relative to isoAsp derivative was observed with decreasing flexibility of the insulin three-dimensional structure in the formulation. In certain crystalline suspensions a cleavage of the peptide bond A8-A9 was observed. Formation of this split product is species dependent: bovine greater than porcine greater than human insulin. The hydrolytic cleavage of the peptide backbone takes place only in preparations containing rhombohedral crystals in addition to free zinc ions.

  1. Stochastic kinetics

    International Nuclear Information System (INIS)

    Colombino, A.; Mosiello, R.; Norelli, F.; Jorio, V.M.; Pacilio, N.

    1975-01-01

    A nuclear system kinetics is formulated according to a stochastic approach. The detailed probability balance equations are written for the probability of finding the mixed population of neutrons and detected neutrons, i.e. detectrons, at a given level for a given instant of time. Equations are integrated in search of a probability profile: a series of cases is analyzed through a progressive criterium. It tends to take into account an increasing number of physical processes within the chosen model. The most important contribution is that solutions interpret analytically experimental conditions of equilibrium (moise analysis) and non equilibrium (pulsed neutron measurements, source drop technique, start up procedures)

  2. Hydrolytic degradation of poly(ethylene oxide)-block-polycaprolactone worm micelles.

    Science.gov (United States)

    Geng, Yan; Discher, Dennis E

    2005-09-21

    Spherical micelles and nanoparticles made with degradable polymers have been of great interest for therapeutic application, but degradation-induced changes in a spherical morphology can be subtle and mechanism/kinetics appears poorly understood. Here, we report the first preparation of giant and flexible worm micelles self-assembled from degradable copolymer poly(ethylene oxide)-block-polycaprolactone. Such worm micelles spontaneously shorten to generate spherical micelles, triggered by polycaprolactone hydrolysis, with distinct mechanism and kinetics from that which occurs in bulk material.

  3. Tolrestat kinetics

    International Nuclear Information System (INIS)

    Hicks, D.R.; Kraml, M.; Cayen, M.N.; Dubuc, J.; Ryder, S.; Dvornik, D.

    1984-01-01

    The kinetics of tolrestat, a potent inhibitor of aldose reductase, were examined. Serum concentrations of tolrestat and of total 14 C were measured after dosing normal subjects and subjects with diabetes with 14 C-labeled tolrestat. In normal subjects, tolrestat was rapidly absorbed and disappearance from serum was biphasic. Distribution and elimination t 1/2s were approximately 2 and 10 to 12 hr, respectively, after single and multiple doses. Unchanged tolrestat accounted for the major portion of 14 C in serum. Radioactivity was rapidly and completely excreted in urine and feces in an approximate ratio of 2:1. Findings were much the same in subjects with diabetes. In normal subjects, the kinetics of oral tolrestat were independent of dose in the 10 to 800 mg range. Repetitive dosing did not result in unexpected cumulation. Tolrestat was more than 99% bound to serum protein; it did not compete with warfarin for binding sites but was displaced to some extent by high concentrations of tolbutamide or salicylate

  4. Hydrolytic Degradation of Poly (ethylene oxide)-block-Polycaprolactone Worm Micelles

    OpenAIRE

    Geng, Yan; Discher, Dennis E.

    2005-01-01

    Spherical micelles and nanoparticles made with degradable polymers have been of great interest for therapeutic application, but degradation induced changes in a spherical morphology can be subtle and mechanism/kinetics appears poorly understood. Here, we report the first preparation of giant and flexible worm micelles self-assembled from degradable copolymer poly (ethylene oxide)-block-polycaprolactone. Such worm micelles spontaneously shorten to generate spherical micelles, triggered by poly...

  5. Investigation on ultrasonication mediated biosurfactant disintegration method in sludge flocs for enhancing hydrolytic enzymes activity and polyhydroxyalkanoates.

    Science.gov (United States)

    Sethupathy, A; Sivashanmugam, P

    2018-06-04

    In this study, a novel biosurfactant potential bacterial strain Pseudomonas pachastrellae RW43 was isolated from pulp and paper sludge and the biosurfactant namely rhamnolipid produced by Pseudomonas pachastrellae RW43 was investigated by varying pH and incubation time in batch liquid fermentation process. The maximal yield of rhamnolipid was found to be 12.1 g/L at an optimized condition of pH 7 and incubation time of 168 h. NMR analysis was performed for identification of molecular structure of produced rhamnolipid and its results concluded that the product was identified as di rhamnolipid. Then, statistically the global optimum conditions for hydrolytic enzymes extraction parameters (sonication power (100 W), extraction time (15 min) and rhamnolipid dosage (2% v/v)) were established. At 30,456 kJ/kg TS specific energy, ultrasonication with rhamnolipid disintegration method extracted maximal consortium activity of hydrolytic enzymes from mixed sludge (municipal and pulp & paper sludge) and the maximum observed were found to be 42.22, 51.75, 34.26, 24.21, 11.35 Units/g VSS respectively for protease, α-amylase, cellulase, lipase and α-glucosidase. Polyhydroxyalkanoates was recovered from enzymes extracted sludge using various solvents namely chloroform, sodium hypochlorite with chloroform and sodium lauryl sulfate with sodium hypochlorite. The maximum recovery was found to be 74 g/kg using sodium hypochlorite and chloroform extraction solvents.

  6. Advances in hexitol and ethylene glycol production by one-pot hydrolytic hydrogenation and hydrogenolysis of cellulose

    International Nuclear Information System (INIS)

    Li, Yuping; Liao, Yuhe; Cao, Xiaofeng; Wang, Tiejun; Ma, Longlong; Long, Jinxing; Liu, Qiying; Xua, Ying

    2015-01-01

    In this review, recent advances in the one-pot hydrolytic hydrogenation and hydrogenolysis of cellulose to value-added polyols, including hexitols (sorbitol, mannitol, and isosorbide) and 1,2-alkanediols (ethylene glycol and 1,2-propylene glycol), are summarized. Methods for the generation of H + in the first step of cellulose hydrolysis to form intermediate sugars, such as the use of soluble acids (mineral acids and heteropoly acids) and H + produced in situ from functional supports and H 2 dissociation, are classified and analyzed, considering its combination with active metals for the subsequent hydrogenation or hydrogenolysis of sugars to polyols. The interaction of non-noble metals such as nickel, bimetals, and tungsten with support materials in the catalytic conversion of intermediate sugars to hexitols and ethylene glycol is reviewed. The corresponding reaction pathways and mechanisms are discussed, including the conversion process using basic supports and solution conditions. Major challenges and promising routes are also suggested for the future development of the chemocatalytic conversion of cellulose. - Highlights: • Advances in the one-pot hydrolytic hydrogenation/hydrogenolysis of cellulose are summarized. • The interaction of non-noble metals with support materials for cellulose conversion is reviewed. • Method for the generation of in situ H + and effects of the acidic groups on supports are discussed. • Incomplete identification of intermediates/products causes mechanism complications. • Efficient conversion, separation and purification are other concerns for cellulose degrading

  7. First derivative spectrophotometric determination of granisetron hydrochloride in presence of its hydrolytic products and preservative and application to pharmaceutical preparations.

    Science.gov (United States)

    Hewala, Ismail I; Bedair, Mona M; Shousha, Sherif M

    2013-04-01

    Granisetron is a selective 5-HT3 receptor antagonist used in prevention and treatment of chemotherapy-induced nausea and vomiting. The drug is available in tablet dosage form and parenteral dosage form containing benzyl alcohol as a preservative. The main route of degradation of granisetron is through hydrolysis. The present work describes the development of a simple, rapid, and reliable first derivative spectrophotometric method for the determination of granisetron in presence of its hydrolytic products as well as the formulations adjuvant and benzyl alcohol. The method is based on the measurement of the first derivative response of granisetron at 290 nm where the interference of the hydrolytic products, the co-formulated adjuvant and benzyl alcohol is completely eliminated. The proposed method was validated with respect to specificity, linearity, selectivity, accuracy, precision, robustness, detection, and quantification limits. Regression analysis showed good correlation between the first derivative response and the concentration of granisetron over a range of 8-16 μg ml(-1) . Statistical analysis proved the accuracy of the proposed method compared with a reference stability indicating high performance liquid chromatography method. The described method was successfully applied to the determination of granisetron in different batches of tablets and ampoules. The assay results obtained in this study strongly encourage us to apply the validated method for the quality control and routine analysis of tablets and parenteral preparations containing granisetron. Copyright © 2012 John Wiley & Sons, Ltd.

  8. Silicon improves seed germination and alleviates drought stress in lentil crops by regulating osmolytes, hydrolytic enzymes and antioxidant defense system.

    Science.gov (United States)

    Biju, Sajitha; Fuentes, Sigfredo; Gupta, Dorin

    2017-10-01

    Silicon (Si) has been widely reported to have beneficial effect on mitigating drought stress in plants. However, the effect of Si on seed germination under drought conditions is still poorly understood. This research was carried out to ascertain the role of Si to abate polyethylene glycol-6000 mediated drought stress on seed germination and seedling growth of lentil. Results showed that drought stress significantly decreased the seed germination traits and increased the concentration of osmolytes (proline, glycine betaine and soluble sugars), reactive oxygen species (hydrogen peroxide and superoxide anion) and lipid peroxides in lentil seedlings. The activities of hydrolytic enzymes and antioxidant enzymes increased significantly under osmotic stress. The application of Si significantly enhanced the plants ability to withstand drought stress conditions through increased Si content, improved antioxidants, hydrolytic enzymes activity, decreased concentration of osmolytes and reactive oxygen species. Multivariate data analysis showed statistically significant correlations among the drought-tolerance traits, whereas cluster analysis categorised the genotypes into distinct groups based on their drought-tolerance levels and improvements in expression of traits due to Si application. Thus, these results showed that Si supplementation of lentil was effective in alleviating the detrimental effects of drought stress on seed germination and increased seedling vigour. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  9. Synthesis,thermal property and hydrolytic degradation of a novel star-shaped hexa[p-(carbonylglycinomethylester)phenoxy]cyclotriphosphazene

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    A novel star-shaped cyclotriphosphazene substituted by glycinomethylesterphenoxy and its intermediates are synthesized from hexachlorocyclotriphosphazene (HCCP). The structures are characterized by 1H NMR,13C NMR,31P NMR,FTIR and elemental analysis. Their thermal properties are clarified by thermogravimetric analysis (TGA),differential scanning calorimentry (DSC) and FTIR,while hydrolytic degradation behaviour is studied with UV-vis spectrophotometer and by measuring the weight loss,and the phosphorus content of residue. According to hydrolysis behaviour of hexa[p-(carbonylglycinomethylester)phenoxy]cyclotriphosphazene (HGPCP) under different conditions,it is easy to hydrolyze in hydrochloric acid (pH 1.0) than in phosphate buffer (pH 7.4) at 37℃. And the sample hydrolytic degradation still remains at the stage of side groups’ break. The TGA data show that the thermal stability of the hexa[p-(aldehyde)phenoxy]cyclotriphosphazene (HAPCP),hexa[p-(carboxyl) phenoxy]cyclotriphosphazene (HCPCP) and HGPCP is so high that their char residues are 75%,47% and 47% at 800℃,respectively,probably due to cross-linking between molecules.

  10. On-site hydrolytic enzymes production from fungal co-cultivation of Bermuda grass and corn cob.

    Science.gov (United States)

    Amaro-Reyes, Aldo; Gracida, Jorge; Huizache-Peña, Nelson; Elizondo-García, Norberto; Salazar-Martínez, José; García Almendárez, Blanca E; Regalado, Carlos

    2016-07-01

    Solid state fermentation (SSF) is used to produce industrial enzymes. The objective of this study was to use a co-culture of Aspergillus niger GS1 and Trichoderma reesei, grown on a mixture of Bermuda grass and corn cob to obtain fermented forage (FF) rich in hydrolytic enzymes, as a value added ingredient for animal feed. FPase, amylase and xylanase productivities (dry matter, DM) were 8.8, 181.4, and 42.1Ug(-1)h(-1), respectively (1U=reducing sugars released min(-1)), after 12-16h of SSF with C/N=60. Cellulose, hemicellulose and lignin decreased 1.6-, 2.7- and 1.9-fold (DM), respectively. In vitro ruminal and true digestibility of DM was improved 2.4- and 1.4-fold. Ruminal digestion of FF reduced 1.32-fold the acetate:propionate ratio, which may reduce the environmental impact of ruminants feeding. On-site hydrolytic enzymes productivity using SSF without enzymes extraction could be of economic potential for digestibility improvement in animal feed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  11. Repair kinetics in tissues

    International Nuclear Information System (INIS)

    Thames, H.D.

    1989-01-01

    Monoexponential repair kinetics is based on the assumption of a single, dose-independent rate of repair of sublethal injury in the target cells for tissue injury after exposure to ionizing radiation. Descriptions of the available data based on this assumption have proved fairly successful for both acutely responding (skin, lip mucosa, gut) and late-responding (lung, spinal cord) normal tissues. There are indications of biphasic exponential repair in both categories, however. Unfortunately, the data usually lack sufficient resolution to permit unambiguous determination of the repair rates. There are also indications that repair kinetics may depend on the size of the dose. The data are conflicting on this account, however, with suggestions of both faster and slower repair after larger doses. Indeed, experiments that have been explicitly designed to test this hypothesis show either no effect (gut, spinal cord), faster repair after higher doses (lung, kidney), or slower repair after higher doses (skin). Monoexponential repair appears to be a fairly accurate description that provides an approximation to a more complicated picture, the elucidation of whose details will, however, require very careful and extensive experimental study. (author). 30 refs.; 1 fig

  12. Multiphasic analysis of gas production kinetics for in vitro fermentation of ruminant feeds.

    NARCIS (Netherlands)

    Groot, J.C.J.; Cone, J.W.; Williams, B.A.; Debersaques, F.M.A.; Lantinga, E.A.

    1996-01-01

    Recently developed time-related gas production techniques to quantify the kinetics of ruminant feed fermentation have a high resolution. Consequently, fermentation processes with clearly contrasting gas production kinetics can be identified. Parameterization of the separate processes is possible

  13. AN INTEGRATED, ANIMATED MODEL OF THE (NA, K-ATPase HYDROLYTIC CYCLE

    Directory of Open Access Journals (Sweden)

    F.A. Leone

    2006-07-01

    Full Text Available The  (Na,  K-ATPase,  or  sodium  pump,  is  the  principal,  active  transport  system  that  establishes  sodium  and potassium  gradients  across  the  plasma  membranes  of  all  animal  cells.  Such  gradients  are  critical  to  sustaining important cellular functions like osmotic equilibrium, cell volume and pH homeostasis, among many others (Ann Rev Physiol 65: 817, 2003; Physiol 19: 377, 2004. This transport protein is a heterodimer that consists of a 110-kDa  -subunit  and  a  55-kDa,  glycosylated  -subunit.  A  group  of  seven  small  proteins,  known  as  FXYD  proteins  from  the sequence  of  a  conserved  motif  has  been  identified  recently,  and  one  of  these,  FXYD2,  constitutes  the  (Na,  K-ATPase  -subunit.  Our  model  is  based  on  conformational  changes  occurring  between  the  E1  and  E2  forms  of  the enzyme, which initiates its hydrolytic cycle at a high ATP/ADP ratio. While all steps are reversible, the model does not include  the reverse  reactions that can  take  place under appropriate conditions. The  E1 state  corresponds to that of the SERCA, recently crystallized (Science 304; 1672, 2004; Nature 430: 529, 2004. The animation was developed in Macromedia  Flash  8.0® and  illustrates  the  principle  of  an  alternating-access  model  of  an  ion  pump.  The  protein  is embedded  in  the  membrane  with  the  extracellular  face  uppermost  and  the  cytoplasmic  face  at  the  bottom.  Access from  the  cytoplasmic  or  extracellular  faces  to  the  cation-binding  sites,  located  in  the  transmembrane  moiety,  are controlled  by  two  gates  (moving  horizontal  bars,  and  conformations  showing  the  two  gates  closed  correspond  to states with occluded Na+ and K+ sites. Changes in cation-binding site structure entail

  14. Reaction kinetics for preparation of silica film with Stoeber method

    International Nuclear Information System (INIS)

    Shang Mengying; Jiang Xiaodong; Liu Miao; Luo Xuan; Tang Yongjian; Cao Linhong

    2013-01-01

    A new formula was proposed to investigate the relationship between reaction time and tetraethylorthosilicate (TEOS) conversion rate for preparation of silica sol with Stöber method, by studying the reaction kinetics of TEOS hydrolytic process. An appropriate conversion rate was then determined and used to calculate the theoretical optimal reaction time. Meanwhile, silica sols were prepared by sol-gel process using TEOS as precursor and ammonia as catalyst. It was found that the reaction time decreases with an increasing amount of ammonia and water. The values of experimental optimal reaction time were obtained, and agree with the theoretical results (the errors are within 5%), which shows good applicability of our formula. (authors)

  15. Nondestructive evaluation of a new hydrolytically degradable and photo-clickable PEG hydrogel for cartilage tissue engineering.

    Science.gov (United States)

    Neumann, Alexander J; Quinn, Timothy; Bryant, Stephanie J

    2016-07-15

    Photopolymerizable and hydrolytically labile poly(ethylene glycol) (PEG) hydrogels formed from photo-clickable reactions were investigated as cell delivery platforms for cartilage tissue engineering (TE). PEG hydrogels were formed from thiol-norbornene PEG macromers whereby the crosslinks contained caprolactone segments with hydrolytically labile ester linkages. Juvenile bovine chondrocytes encapsulated in the hydrogels were cultured for up to four weeks and assessed biochemically and histologically, using standard destructive assays, and for mechanical and ultrasound properties, as nondestructive assays. Bulk degradation of acellular hydrogels was confirmed by a decrease in compressive modulus and an increase in mass swelling ratio over time. Chondrocytes deposited increasing amounts of sulfated glycosaminoglycans and collagens in the hydrogels with time. Spatially, collagen type II and aggrecan were present in the neotissue with formation of a territorial matrix beginning at day 21. Nondestructive measurements revealed an 8-fold increase in compressive modulus from days 7 to 28, which correlated with total collagen content. Ultrasound measurements revealed changes in the constructs over time, which differed from the mechanical properties, and appeared to correlate with ECM structure and organization shown by immunohistochemical analysis. Overall, non-destructive and destructive measurements show that this new hydrolytically degradable PEG hydrogel is promising for cartilage TE. Designing synthetic hydrogels whose degradation matches tissue growth is critical to maintaining mechanical integrity as the hydrogel degrades and new tissue forms, but is challenging due to the nature of the hydrogel crosslinks that inhibit diffusion of tissue matrix molecules. This study details a promising, new, photo-clickable and synthetic hydrogel whose degradation supports cartilaginous tissue matrix growth leading to the formation of a territorial matrix, concomitant with an

  16. A Selective High Performance Liquid Chromatographic Method to Follow the Hydrolytic Degradation of Nicardipine Hydrochloride

    Directory of Open Access Journals (Sweden)

    K. E. Ibrahim

    2010-01-01

    Full Text Available A simple, stability indicating, reverse phase high performance liquid chromatographic method was developed and validated for determination of nicardipine hydrochloride (NC in the presence of its degradation products. The chromatographic separation was performed on Hypersil, BDS-C18, 30 cm × 3.9 mm id, at ambient temperature with UV-detection at 254 nm. A mixture of 20% (v/v aqueous 0.01 M sodium acetate∕acetic acid buffer (pH 4.5 and 80% acetonitrile was used as the mobile phase at a flow rate of 1.5 mL min-1, losartan was used as internal standard. The calibration curve is linear over the concentration range 5-40 μg mL-1, with a regression coefficient of 0.9984 and the % recovery was 99.78±0.17. The method was used to investigate the kinetics of alkaline, acids induced degradation, effect of buffer concentration and temperature. The degradation followed first-order kinetics. The rate constant, half-life time, and activation energy were calculated

  17. Gibbs Free Energy of Hydrolytic Water Molecule in Acyl-Enzyme Intermediates of a Serine Protease: A Potential Application for Computer-Aided Discovery of Mechanism-Based Reversible Covalent Inhibitors.

    Science.gov (United States)

    Masuda, Yosuke; Yamaotsu, Noriyuki; Hirono, Shuichi

    2017-01-01

    In order to predict the potencies of mechanism-based reversible covalent inhibitors, the relationships between calculated Gibbs free energy of hydrolytic water molecule in acyl-trypsin intermediates and experimentally measured catalytic rate constants (k cat ) were investigated. After obtaining representative solution structures by molecular dynamics (MD) simulations, hydration thermodynamics analyses using WaterMap™ were conducted. Consequently, we found for the first time that when Gibbs free energy of the hydrolytic water molecule was lower, logarithms of k cat were also lower. The hydrolytic water molecule with favorable Gibbs free energy may hydrolyze acylated serine slowly. Gibbs free energy of hydrolytic water molecule might be a useful descriptor for computer-aided discovery of mechanism-based reversible covalent inhibitors of hydrolytic enzymes.

  18. Resolution propositions

    International Nuclear Information System (INIS)

    2003-05-01

    To put a resolution to the meeting in relation with the use of weapons made of depleted uranium is the purpose of this text. The situation of the use of depleted uranium by France during the Gulf war and other recent conflicts will be established. This resolution will give the most strict recommendations face to the eventual sanitary and environmental risks in the use of these kind of weapons. (N.C.)

  19. Fabrication of hollow silica–zirconia composite spheres and their activity for hydrolytic dehydrogenation of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Umegaki, Tetsuo, E-mail: umegaki.tetsuo@nihon-u.ac.jp [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Hosoya, Tatsuya; Toyama, Naoki [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Xu, Qiang [National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Kojima, Yoshiyuki [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan)

    2014-09-01

    Highlights: • Hollow silica–zirconia composite spheres were fabricated on polystyrene templates by the sol–gel method. • We study the effect of preparation conditions on the activity for hydrolytic dehydrogenation of ammonia borane. • The activity of hollow silica–zirconia composite spheres depends on wall thickness. - Abstract: In this paper, we report fabrication of hollow silica–zirconia composite spheres by polystyrene (PS) template method and control of wall thickness of the hollow spheres in nanoscale. Both the hollow spheres before and after calcination were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), elemental analysis, and powder X-ray diffraction analysis (XRD). Morphology of the hollow spheres does not significantly change after calcination from the results of SEM and TEM images, while the amount of residual PS templates drastically decreases via the calcination procedure from the results of FTIR and elemental analysis. The sample after calcination mainly includes amorphous silica from the results of XRD, indicating that the hollow silica–zirconia composite spheres consist of amorphous phases and/or fine particles. Wall thicknesses of the samples after calcination are controlled by adjusting the amount of PS template suspension, and hollow silica–zirconia composite spheres with the wall thicknesses of 17.5, 15.0, 10.0, and 2.0 nm are obtained using the PS template suspension of 25.0, 33.5, 100.0, and 400.0 g, respectively. The activities of the hollow spheres for hydrolytic dehydrogenation of ammonia borane (NH{sub 3}BH{sub 3}) were compared. The evolutions of 2.0, 3.1, 5.0, and 8.0 mL hydrogen from aqueous NH{sub 3}BH{sub 3} solution were finished in about 4, 5, 3, and 7 min in the presence of the hollow spheres with wall thicknesses of 17.5, 15.0, 10.0, and 2.0 nm, respectively. The molar ratios of the hydrolytically generated hydrogen to

  20. Synthesis, Properties, and In Vitro Hydrolytic Degradation of Poly(d,l-lactide-co-glycolide-co-ε-caprolactone

    Directory of Open Access Journals (Sweden)

    Yixiu Liu

    2016-01-01

    Full Text Available Random copolymers of poly(d,l-lactide-co-glycolide-co-ε-caprolactone (PLGC were synthesized by the ring-opening polymerization of d,l-lactide (DLLA, glycolide (GA, and ε-caprolactone (CL. The effects of CL on the copolymers were evaluated to prepare suitable copolymers with controlled properties. Our results showed that the CL content significantly influenced the thermal and mechanical properties of the copolymers and that the CL content in compositions could be altered to control properties of random copolymers. The in vitro hydrolytic degradation of the resulting implants showed that the degradation rate of PLGC was lower than that of PLGA, which could markedly reduce acidic degradation products. Finally, we demonstrated that higher CL contents in compositions slowed degradation rates.

  1. The influence of the length of the degradable segment on the functional properties and hydrolytic stability of multi-component polyurethane elastomeric films

    Czech Academy of Sciences Publication Activity Database

    Špírková, Milena; Hodan, Jiří; Kobera, Libor; Kredatusová, Jana; Kubies, Dana; Machová, Luďka; Poreba, Rafal; Serkis, Magdalena; Zhigunov, Alexander; Kotek, Jiří

    2017-01-01

    Roč. 137, March (2017), s. 216-228 ISSN 0141-3910 R&D Projects: GA ČR(CZ) GA13-06700S Institutional support: RVO:61389013 Keywords : polyurethane elastomer * lactide * hydrolytic degradation Subject RIV: CD - Macromolecular Chemistry OBOR OECD: Polymer science Impact factor: 3.386, year: 2016

  2. Thermomyces lanuginosus STm: a source of thermostable hydrolytic enzymes for novel application in extraction of high-quality natural rubber from Taraxacum kok-saghyz (rubber dandelion)

    Science.gov (United States)

    Hydrolytic enzymes from a newly isolated strain of the thermophilic fungus Thermomyces lanuginosus were used to extract rubber from Taraxacum kok-saghyz commonly known as rubber (or Russian or Kazak(h)) dandelion. The fungus was isolated from garden soil and identified as Thermomyces lanuginosus STm...

  3. Hydrolytic enzymes production by Aspergillus section Nigri in presence of butylated hydroxyanisole and propyl paraben on peanut meal extract agar.

    Science.gov (United States)

    Barberis, Carla L; Landa, María F; Barberis, Mauricio G; Giaj-Merlera, Guillermo; Dalcero, Ana M; Magnoli, Carina E

    2014-01-01

    In the last years, food grade antioxidants are used safely as an alternative to traditional fungicides to control fungal growth in several food and agricultural products. In this work, the effect of butylated hydroxyanisole (BHA) and propyl paraben (PP) on two hydrolytic enzyme activity (β-d-glucosidase and α-d-galactosidase) by Aspergillus section Nigri species under different water activity conditions (aW; 0.98, 0.95 and 0.93) and incubation time intervals (24, 48, 72 and 96h) was evaluated on peanut-based medium. The activity of two glycosidases, β-d-glucosidase and α-d-galactosidase, was assayed using as substrates 4-nitrophenyl-β-d-glucopyranosido and 4-nitrophenyl-α-d-galactopyranosido, respectively. The enzyme activity was determined by the increase in optical density at 405nm caused by the liberation of p-nitrophenol by enzymatic hydrolysis of the substrate. Enzyme activity was expressed as micromoles of p-nitrophenol released per minute. The major inhibition in β-d-glucosidase activity of A. carbonarius and A. niger was found with 20mmoll(-1) of BHA or PP at 0.98 and 0.95 aW, respectively, whereas for α-d-galactosidase activity a significant decrease in enzyme activity with respect to control was observed in A. carbonarius among 5 to 20mmoll(-1) of BHA or PP in all conditions assayed. Regarding A. niger, the highest percentages of enzyme inhibition activity were found with 20mmoll(-1) of BHA or PP at 0.95 aW and 96h. The results of this work provide information about the capacity of BHA and PP to inhibit in vitro conditions two of the most important hydrolytic enzymes produced by A. carbonarius and A. niger species. Copyright © 2012 Revista Iberoamericana de Micología. Published by Elsevier Espana. All rights reserved.

  4. Quantitative phase analysis and microstructure characterization of magnetite nanocrystals obtained by microwave assisted non-hydrolytic sol–gel synthesis

    International Nuclear Information System (INIS)

    Sciancalepore, Corrado; Bondioli, Federica; Manfredini, Tiziano; Gualtieri, Alessandro

    2015-01-01

    An innovative preparation procedure, based on microwave assisted non-hydrolytic sol–gel synthesis, to obtain spherical magnetite nanoparticles was reported together with a detailed quantitative phase analysis and microstructure characterization of the synthetic products. The nanoparticle growth was analyzed as a function of the synthesis time and was described in terms of crystallization degree employing the Rietveld method on the magnetic nanostructured system for the determination of the amorphous content using hematite as internal standard. Product crystallinity increases as the microwave thermal treatment is increased and reaches very high percentages for synthesis times longer than 1 h. Microstructural evolution of nanocrystals was followed by the integral breadth methods to obtain information on the crystallite size-strain distribution. The results of diffraction line profile analysis were compared with nanoparticle grain distribution estimated by dimensional analysis of the transmission electron microscopy (TEM) images. A variation both in the average grain size and in the distribution of the coherently diffraction domains is evidenced, allowing to suppose a relationship between the two quantities. The traditional integral breadth methods have proven to be valid for a rapid assessment of the diffraction line broadening effects in the above-mentioned nanostructured systems and the basic assumption for the correct use of these methods are discussed as well. - Highlights: • Fe 3 O 4 nanocrystals were obtained by MW-assisted non-hydrolytic sol–gel synthesis. • Quantitative phase analysis revealed that crystallinity up to 95% was reached. • The strategy of Rietveld refinements was discussed in details. • Dimensional analysis showed nanoparticles ranging from 4 to 8 nm. • Results of integral breadth methods were compared with microscopic analysis

  5. Quantitative phase analysis and microstructure characterization of magnetite nanocrystals obtained by microwave assisted non-hydrolytic sol–gel synthesis

    Energy Technology Data Exchange (ETDEWEB)

    Sciancalepore, Corrado, E-mail: corrado.sciancalepore@unimore.it [Department of Engineering “Enzo Ferrari”, University of Modena and Reggio Emilia, Via Pietro Vivarelli 10, 41100 Modena (Italy); Bondioli, Federica [Department of Industrial Engineering, University of Parma, Parco Area delle Scienze, 181/A, 43124 Parma (Italy); INSTM Consortium, Via G. Giusti 9, 51121 Firenze (Italy); Manfredini, Tiziano [Department of Engineering “Enzo Ferrari”, University of Modena and Reggio Emilia, Via Pietro Vivarelli 10, 41100 Modena (Italy); INSTM Consortium, Via G. Giusti 9, 51121 Firenze (Italy); Gualtieri, Alessandro [Department of Chemical and Geological Science, University of Modena and Reggio Emilia, Via S. Eufemia 19, 41121 Modena Italy (Italy)

    2015-02-15

    An innovative preparation procedure, based on microwave assisted non-hydrolytic sol–gel synthesis, to obtain spherical magnetite nanoparticles was reported together with a detailed quantitative phase analysis and microstructure characterization of the synthetic products. The nanoparticle growth was analyzed as a function of the synthesis time and was described in terms of crystallization degree employing the Rietveld method on the magnetic nanostructured system for the determination of the amorphous content using hematite as internal standard. Product crystallinity increases as the microwave thermal treatment is increased and reaches very high percentages for synthesis times longer than 1 h. Microstructural evolution of nanocrystals was followed by the integral breadth methods to obtain information on the crystallite size-strain distribution. The results of diffraction line profile analysis were compared with nanoparticle grain distribution estimated by dimensional analysis of the transmission electron microscopy (TEM) images. A variation both in the average grain size and in the distribution of the coherently diffraction domains is evidenced, allowing to suppose a relationship between the two quantities. The traditional integral breadth methods have proven to be valid for a rapid assessment of the diffraction line broadening effects in the above-mentioned nanostructured systems and the basic assumption for the correct use of these methods are discussed as well. - Highlights: • Fe{sub 3}O{sub 4} nanocrystals were obtained by MW-assisted non-hydrolytic sol–gel synthesis. • Quantitative phase analysis revealed that crystallinity up to 95% was reached. • The strategy of Rietveld refinements was discussed in details. • Dimensional analysis showed nanoparticles ranging from 4 to 8 nm. • Results of integral breadth methods were compared with microscopic analysis.

  6. Synthesis and photoluminescent properties of yttrium vanadate phosphor prepared by the non-hydrolytic sol–gel process

    International Nuclear Information System (INIS)

    Matos, Marcela G.; Faria, Emerson H. de; Rocha, Lucas A.; Calefi, Paulo S.; Ciuffi, Katia J.; Nassar, Eduardo J.; Sarmento, Victor Hugo Vitorino

    2014-01-01

    We used the non-hydrolytic sol–gel route to synthesize YVO 4 crystalline phases doped with europium III ion. We heat-treated the samples at 600, 800, and 1000 °C and characterized the materials by thermal analysis, X-ray diffraction, small-angle X-ray scattering, and photoluminescence. Larger weight loss occurred until 500 °C, ascribed to removal of residual precursor molecules. X-ray diffraction patterns evidenced YVO 4 phase formation at 600 °C. The crystallite size depended on the heat treatment temperature. SAXS showed that the nature of the system interfaces changed as a function of the thermal treatment. The excitation spectra of the samples displayed the charge transfer band. The photoluminescence data revealed the characteristic transition bands arising from the 5 D 0 → 5 F J (J=0, 1, 2, 3, and 4) manifolds under maximum excitation at the charge transfer band and the 5 L 6 level of the Eu 3+ ion. The 5 D 0 → 7 F 2 transition dominated the emission spectra, indicating that the Eu 3+ ion occupies a site without inversion center. The lifetime and quantum efficiency values were about 0.70 ms and 50%, respectively, corroborating literature results. -- Highlights: • This study described the preparation of the yttrium vanadate by non-hydrolytic sol–gel. • The SAXS curves can be interpreted from the fractal theory for a two-phase model. • The goal of the work is the preparation of the phosphors at low temperature. • The lifetimes depend on wavelength of the excitation

  7. Synthesis and photoluminescent properties of yttrium vanadate phosphor prepared by the non-hydrolytic sol–gel process

    Energy Technology Data Exchange (ETDEWEB)

    Matos, Marcela G.; Faria, Emerson H. de; Rocha, Lucas A.; Calefi, Paulo S.; Ciuffi, Katia J. [Universidade de Franca, Av. Dr. Armando Salles Oliveira, 201 Franca, SP, CEP 14404-600 (Brazil); Nassar, Eduardo J., E-mail: ejnassar@unifran.br [Universidade de Franca, Av. Dr. Armando Salles Oliveira, 201 Franca, SP, CEP 14404-600 (Brazil); Sarmento, Victor Hugo Vitorino [Universidade Federal de Sergipe, Av. Ver. Olimpio Grande s/n Itabaiana, SE, CEP 49500-000 (Brazil)

    2014-03-15

    We used the non-hydrolytic sol–gel route to synthesize YVO{sub 4} crystalline phases doped with europium III ion. We heat-treated the samples at 600, 800, and 1000 °C and characterized the materials by thermal analysis, X-ray diffraction, small-angle X-ray scattering, and photoluminescence. Larger weight loss occurred until 500 °C, ascribed to removal of residual precursor molecules. X-ray diffraction patterns evidenced YVO{sub 4} phase formation at 600 °C. The crystallite size depended on the heat treatment temperature. SAXS showed that the nature of the system interfaces changed as a function of the thermal treatment. The excitation spectra of the samples displayed the charge transfer band. The photoluminescence data revealed the characteristic transition bands arising from the {sup 5}D{sub 0}→{sup 5}F{sub J} (J=0, 1, 2, 3, and 4) manifolds under maximum excitation at the charge transfer band and the {sup 5}L{sub 6} level of the Eu{sup 3+} ion. The {sup 5}D{sub 0}→{sup 7}F{sub 2} transition dominated the emission spectra, indicating that the Eu{sup 3+} ion occupies a site without inversion center. The lifetime and quantum efficiency values were about 0.70 ms and 50%, respectively, corroborating literature results. -- Highlights: • This study described the preparation of the yttrium vanadate by non-hydrolytic sol–gel. • The SAXS curves can be interpreted from the fractal theory for a two-phase model. • The goal of the work is the preparation of the phosphors at low temperature. • The lifetimes depend on wavelength of the excitation.

  8. The eddy kinetic energy budget in the Red Sea

    KAUST Repository

    Zhan, Peng; Subramanian, Aneesh C.; Yao, Fengchao; Kartadikaria, Aditya R.; Guo, Daquan; Hoteit, Ibrahim

    2016-01-01

    The budget of eddy kinetic energy (EKE) in the Red Sea, including the sources, redistributions and sink, is examined using a high-resolution eddy-resolving ocean circulation model. A pronounced seasonally varying EKE is identified, with its maximum

  9. Production in Pichia pastoris, antifungal activity and crystal structure of a class I chitinase from cowpea (Vigna unguiculata): Insights into sugar binding mode and hydrolytic action.

    Science.gov (United States)

    Landim, Patrícia G Castro; Correia, Tuana O; Silva, Fredy D A; Nepomuceno, Denise R; Costa, Helen P S; Pereira, Humberto M; Lobo, Marina D P; Moreno, Frederico B M B; Brandão-Neto, José; Medeiros, Suelen C; Vasconcelos, Ilka M; Oliveira, José T A; Sousa, Bruno L; Barroso-Neto, Ito L; Freire, Valder N; Carvalho, Cristina P S; Monteiro-Moreira, Ana C O; Grangeiro, Thalles B

    2017-04-01

    A cowpea class I chitinase (VuChiI) was expressed in the methylotrophic yeast P. pastoris. The recombinant protein was secreted into the culture medium and purified by affinity chromatography on a chitin matrix. The purified chitinase migrated on SDS-polyacrylamide gel electrophoresis as two closely-related bands with apparent molecular masses of 34 and 37 kDa. The identity of these bands as VuChiI was demonstrated by mass spectrometry analysis of tryptic peptides and N-terminal amino acid sequencing. The recombinant chitinase was able to hydrolyze colloidal chitin but did not exhibit enzymatic activity toward synthetic substrates. The highest hydrolytic activity of the cowpea chitinase toward colloidal chitin was observed at pH 5.0. Furthermore, most VuChiI activity (approximately 92%) was retained after heating to 50 °C for 30 min, whereas treatment with 5 mM Cu 2+ caused a reduction of 67% in the enzyme's chitinolytic activity. The recombinant protein had antifungal activity as revealed by its ability to inhibit the spore germination and mycelial growth of Penicillium herquei. The three-dimensional structure of VuChiI was resolved at a resolution of 1.55 Å by molecular replacement. The refined model had 245 amino acid residues and 381 water molecules, and the final R-factor and R free values were 14.78 and 17.22%, respectively. The catalytic domain of VuChiI adopts an α-helix-rich fold, stabilized by 3 disulfide bridges and possessing a wide catalytic cleft. Analysis of the crystallographic model and molecular docking calculations using chito-oligosaccharides provided evidences about the VuChiI residues involved in sugar binding and catalysis, and a possible mechanism of antifungal action is suggested. Copyright © 2017 Elsevier B.V. and Société Française de Biochimie et Biologie Moléculaire (SFBBM). All rights reserved.

  10. Design, Synthesis and Hydrolytic Behavior of Mutual Prodrugs of NSAIDs with Gabapentin Using Glycol Spacers

    Directory of Open Access Journals (Sweden)

    Hiba Najeh Alsaad

    2012-10-01

    Full Text Available The free –COOH present in NSAIDs is thought to be responsible for the GI irritation associated with all traditional NSAIDs. Exploitation of mutual prodrugs is an approach wherein the NSAID is covalently bounded to a second pharmacologically active carrier/drug with the ultimate aim of reducing the gastric irritation. In this study some NSAIDs were conjugated with gabapentin via ester bonds using glycol spacers with the expectation of reducing gastric adverse effects and obtaining synergistic analgesic effects. The kinetics of ester hydrolysis were studied in two different non enzymatic buffer solutions at pH 1.2 and 7.4, as well as in 80% human plasma using HPLC with chloroform -methanol as mobile phase. Compounds 9a–c with ethylene glycol spacers showed significant stability at buffer solutions with half lives ranging from about 8–25 h, while the underwent a reasonable plasma hydrolysis (49%–88% in 2 h. Compound 9d with a propylene glycol spacer shows a higher rate of enzymatic hydrolysis than the corresponding ethylene glycol compound 9c. The result of compounds 9a-c indicate that these compounds may be stable during their passage through the GIT until reaching the blood circulation.

  11. Cesium removal and kinetics equilibrium: Precipitation kinetics

    International Nuclear Information System (INIS)

    Barnes, M.J.

    1999-01-01

    This task consisted of both non-radioactive and radioactive (tracer) tests examining the influence of potentially significant variables on cesium tetraphenylborate precipitation kinetics. The work investigated the time required to reach cesium decontamination and the conditions that affect the cesium precipitation kinetics

  12. Plasma kinetic theory

    International Nuclear Information System (INIS)

    Elliott, J.A.

    1993-01-01

    Plasma kinetic theory is discussed and a comparison made with the kinetic theory of gases. The plasma is described by a modified set of fluid equations and it is shown how these fluid equations can be derived. (UK)

  13. Lipase Catalyzed Kinetic Resolution of rac-2-(3-Methoxy-4-methylphenyl) propan-1-ol and rac-2-(3-Hydroxy-4-methylphenyl)propyl propanoate for S-(+)-Xanthorrhizol

    International Nuclear Information System (INIS)

    Shafioul, Azam Sharif Mohammed; Cheong, Chan Seong

    2012-01-01

    Xanthorrhizol is a bisabolane type of natural sesquiterpene, the major component of essential oils of Curcuma xanthorrhiza. 2-(3-Methoxy-4-methylphenyl)propan-1-ol and 2-(3-hydroxy-4-methyl phenyl)propan-1-ol could be essential building block for enantioselective synthesis of xanthorrhizol. Enantioselective (c = 53%, E = 80 ± 3) for R-(+)-2-(3-hydroxy-4-methylphenyl) propan-1-ol and (c = 58%, E = 27 ± 1) for R-(+)-2-(3- methoxy-4-methylphenyl) propan-1-ol resolution processes were developed via lipase-catalyzed reaction. We found lipase Aspergillus oryzae (AOL) and Porcine pancreas (PPL) are selective to transesterification and hydrolysis in organic and aqueous phase. Modified demethylated substrate is appropriate for enantioselective hydrolysis reaction without any additives. Enantiopure chiral alcohol was crystallized from ethyl acetate/ n-hexane co-solvent system. Gram scale resolved chiral intermediate will facilitate the synthesis of the unnatural S-(+)-xanthorrhizol, the corresponding isomer of the natural one

  14. Lipase Catalyzed Kinetic Resolution of rac-2-(3-Methoxy-4-methylphenyl) propan-1-ol and rac-2-(3-Hydroxy-4-methylphenyl)propyl propanoate for S-(+)-Xanthorrhizol

    Energy Technology Data Exchange (ETDEWEB)

    Shafioul, Azam Sharif Mohammed [University of Science and Technology, Daejeon (Korea, Republic of); Cheong, Chan Seong [Korea Institute of Science and Technology, Seoul (Korea, Republic of)

    2012-02-15

    Xanthorrhizol is a bisabolane type of natural sesquiterpene, the major component of essential oils of Curcuma xanthorrhiza. 2-(3-Methoxy-4-methylphenyl)propan-1-ol and 2-(3-hydroxy-4-methyl phenyl)propan-1-ol could be essential building block for enantioselective synthesis of xanthorrhizol. Enantioselective (c = 53%, E = 80 ± 3) for R-(+)-2-(3-hydroxy-4-methylphenyl) propan-1-ol and (c = 58%, E = 27 ± 1) for R-(+)-2-(3- methoxy-4-methylphenyl) propan-1-ol resolution processes were developed via lipase-catalyzed reaction. We found lipase Aspergillus oryzae (AOL) and Porcine pancreas (PPL) are selective to transesterification and hydrolysis in organic and aqueous phase. Modified demethylated substrate is appropriate for enantioselective hydrolysis reaction without any additives. Enantiopure chiral alcohol was crystallized from ethyl acetate/ n-hexane co-solvent system. Gram scale resolved chiral intermediate will facilitate the synthesis of the unnatural S-(+)-xanthorrhizol, the corresponding isomer of the natural one.

  15. Solubilization of low-rank coal by Trichoderma atroviride: Evidence for the involvement of hydrolytic and oxidative enzymes by using C-14-labelled lignite

    Energy Technology Data Exchange (ETDEWEB)

    Holker, U.; Schmiers, H.; Grosse, S.; Winkelhofer, M.; Polsakiewicz, M.; Ludwig, S.; Dohse, J.; Hofer, M. [University of Bonn, Bonn (Germany). Inst. of Botany

    2002-04-01

    The deuteromycete Trichoderma atroviride is able to solubilize lignite in dependence on a given carbon source for growth. When cultivated on media containing glutamate, this mold excreted a set of different enzymes with hydrolytic activity. Addition of lignite to the growth media induced the synthesis of extracellular lignite-specific esterase activity but no evidence has been provided for its direct involvement in the process of lignite solubilization. Hence, the basic capability of T. atroviride enzymes to degrade a variety of ester and ether bonds at the surface or within the bulky lignite structure was tested using coal following its direct labelling with C-14-alkyl iodide. The participation of hydrolytic and oxidative enzymes in lignite degradation was assessed by measuring the release of C-14 radioactivity from selectively alkylated carboxylic and phenolic OH groups. T. atroviride cleaved both carboxylic esters using esterases and the phenolic ether bonds by using oxidative enzymes, most likely laccases.

  16. Hydrolytic study of the copolymer Poly pyrrole/ Polyethyleneglycol and Poly pyrrole synthesized by plasma; Estudio hidrolitico del copolimero polipirrol/polietilenglicol y polipirrol sintetizado por plasma

    Energy Technology Data Exchange (ETDEWEB)

    Colin, E.; Enriquez, M.A.; Olayo, M.G.; Cruz, G.J.; Carapia, L.; Romero, M. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico); Morales, J.; Olayo, R. [UAM-I, A.P. 55-534 Iztapalapa, Mexico D.F. (Mexico)

    2006-07-01

    In this work the study about the hydrolytic compatibility of semiconductor polymers, copolymer Poly pyrrole/ Polyethyleneglycol (PPy/PEG) and Poly pyrrole (PPy) for their possible use as biomaterials. The polymers were synthesized by plasma between 10 and 100 W, with discharges of splendor RF to 13.5 MHz with resistive coupling. The hydrolytic affinity was evaluated calculating the contact angle with solutions of NaCl, NaCl-MgSO{sub 4} and Krebs-Ringer. The results show a hydrophilicity increment due to the increase of the surface ruggedness with the synthesis energy. On the contrary, the crystallinity diminishes when increasing the power in PPy and it stays approximately constant in PPy/PEG. The electric conductivity presents a growth from 2 to 4 magnitude orders in function of the water content in the polymers. (Author)

  17. Preparation of bimetallic Cu-Co nanocatalysts on poly (diallyldimethylammonium chloride) functionalized halloysite nanotubes for hydrolytic dehydrogenation of ammonia borane

    Science.gov (United States)

    Liu, Yang; Zhang, Jun; Guan, Huijuan; Zhao, Yafei; Yang, Jing-He; Zhang, Bing

    2018-01-01

    In present work, we prepared the bimetallic Cu-Co nanocatalysts on poly (diallyldimethylammonium chloride) functionalized halloysite nanotubes (Cu-Co/PDDA-HNTs) by a deposition-reduction technique at room temperature. The analysis of XRD, SEM, TEM, HAADF-STEM and XPS were employed to systematically investigate the morphology, particle size, structure and surface properties of the nanocomposite. The results reveal that the PDDA coating with thickness of ∼15 nm could be formed on the surface of HNTs, and the existence of PDDA is beneficial to deposit Cu and Co nanoparticles (NPs) with high dispersibility on the surface. While the cost-effective nanocomposite was used for the hydrolytic dehydrogenation of ammonia-borane (NH3BH3), the nanocatalyst showed extraordinary catalytic properties with high total turnover frequency of 30.8 molH2/(molmetal min), low activation energy of 35.15 kJ mol-1 and high recycling stability (>90% conversion at 10th reuse). These results indicate that the bimetallic Cu-Co nanocatalysts on PDDA functionalized HNTs have particular potential for application in release hydrogen process.

  18. Production of chlorothalonil hydrolytic dehalogenase from agro-industrial wastewater and its application in raw food cleaning.

    Science.gov (United States)

    He, Qin; Xu, Xi-Hui; Zhang, Fan; Tai, Yu-Kai; Luo, Yan-Fei; He, Jian; Hong, Qing; Jiang, Jian-Dong; Yan, Xin

    2017-06-01

    To reduce the fermentation cost for industrialization of chlorothalonil hydrolytic dehalogenase (Chd), agro-industrial wastewaters including molasses, corn steep liquor (CSL) and fermentation wastewater were used to substitute for expensive carbon and nitrogen sources and fresh water for lab preparation. The results showed that molasses and CSL could replace 5% carbon source and 100% organic nitrogen source respectively to maintain the same fermentation level. Re-fermentation from raffinate of ultra-filtered fermentation wastewater could achieve 61.03% of initial Chd activity and reach 96.39% activity when cultured in a mixture of raffinate and 50% of original medium constituent. Typical raw foods were chosen to evaluate the chlorothalonil removal ability of Chd. After Chd treatment for 2 h at room temperature, 97.40 and 75.55% of 30 mg kg -1 chlorothalonil on cherry tomato and strawberry respectively and 60.29% of 50 mg kg -1 chlorothalonil on Chinese cabbage were removed. Furthermore, the residual activity of the enzyme remained at 78-82% after treatment, suggesting its potential for reuse. This study proved the cost-feasibility of large-scale production of Chd from agro-industrial wastewater and demonstrated the potential of Chd in raw food cleaning. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  19. Application of a novel enzymatic pretreatment using crude hydrolytic extracellular enzyme solution to microalgal biomass for dark fermentative hydrogen production.

    Science.gov (United States)

    Yun, Yeo-Myeong; Kim, Dong-Hoon; Oh, You-Kwan; Shin, Hang-Sik; Jung, Kyung-Won

    2014-05-01

    In this study, a novel enzymatic pretreatment of Chlorella vulgaris for dark fermentative hydrogen production (DFHP) was performed using crude hydrolytic extracellular enzyme solution (CHEES) extracted from the H2 fermented effluent of food waste. It was found that the enzyme extracted at 52 h had the highest hydrolysis efficiency of microalgal biomass, resulting in the highest H2 yield of 43.1 mL H2/g dry cell weight along with shorter lag periods. Even though a high amount of VFAs was accumulated in CHEES, especially butyrate, the fermentative bacteria on the DFHP was not affected from product inhibition. It also appears that the presence of organic acids, especially lactate and acetate, contained in the CHEES facilitated enhancement of H2 production acted as a co-substrate. Therefore, all of the experimental results suggest that the enhancement of DFHP performance caused by CHEES has a dual role as the hydrolysis enhancer and the co-substrate supplier. Copyright © 2014 Elsevier Ltd. All rights reserved.

  20. Hydrolytic stability of three-step etch-and-rinse adhesives in occlusal class-I cavities.

    Science.gov (United States)

    De Munck, Jan; Mine, Atsushi; Vivan Cardoso, Marcio; Van Landuyt, Kirsten L; Lührs, Anne-Katrin; Poitevin, André; Hanabusa, Masao; Kuboki, Takuo; Van Meerbeek, Bart

    2013-11-01

    A dental adhesive without small and hydrophilic monomers such as 2-hydroxyethyl methacrylate (HEMA) and triethylene glycol dimethacrylate (TEGDMA) would be beneficial in order to avoid contact allergies. However, these monomers are important to increase infiltration and polymerization of the adhesive. Therefore, the purpose of this study was to evaluate the bonding effectiveness and bond durability of a more hydrophobic and biocompatible adhesive as compared to a conventional three-step etch-and-rinse adhesive. Sixteen non-carious human third molars were used to determine the micro-tensile bond strength testing (μTBS) and interfacial ultrastructure by transmission electron microscopy (TEM) of the more hydrophobic cmf adhesive system (Saremco) adhesive as compared to the control OptiBond FL (Kerr). The more hydrophobic and biocompatible three-step etch-and-rinse adhesive was able to produce a reasonable short-time bonding effectiveness. In the long term, the collagen fibrils in the hybrid layer were not effectively protected and were prone to hydrolytic degradation. As a result, long-term bonding effectiveness of this novel adhesive was very low. Application of a more hydrophobic adhesive without altering the application procedure considerably results in a reduced durability of the created bond Omitting small and hydrophilic components from the adhesive formulation may impair the durability of your composite restoration.

  1. Long term effect of alkali types on waste activated sludge hydrolytic acidification and microbial community at low temperature.

    Science.gov (United States)

    Jin, Baodan; Wang, Shuying; Xing, Liqun; Li, Baikun; Peng, Yongzhen

    2016-01-01

    The effect of four alkali reagents (NaOH, KOH, Ca(OH)2, mixed alkali) on waste activated sludge (WAS) hydrolytic acidification and microbial community was studied in semi-continuous fermentation systems at low temperature (15°C) over long term operational time (65day). The results showed that protein and polysaccharide of NaOH (124.26, 11.92) was similar to that of KOH (109.53, 11.30), both were higher than Ca(OH)2 (70.66, 3.74) and mixed alkali (90.66, 8.71). The short chain fatty acids (SCFAs) of NaOH (231.62) was higher than KOH (220.62mg chemical oxygen demand (COD)/g VSS). Although Ca(OH)2 system had strong acidification capacity, the shortage of SCFAs occurred due to the low activity of hydrolase. Illumina MiSeq sequencing revealed that Tissierella and Erysipelothrix were enriched in the NaOH and Ca(OH)2 systems, where Peptostreptococcaceae incertae_sedis was enriched in the NaOH and KOH systems, less Anaerolinea was involved in Ca(OH)2 condition. Copyright © 2015. Published by Elsevier Ltd.

  2. Mechanical behaviour׳s evolution of a PLA-b-PEG-b-PLA triblock copolymer during hydrolytic degradation.

    Science.gov (United States)

    Breche, Q; Chagnon, G; Machado, G; Girard, E; Nottelet, B; Garric, X; Favier, D

    2016-07-01

    PLA-b-PEG-b-PLA is a biodegradable triblock copolymer that presents both the mechanical properties of PLA and the hydrophilicity of PEG. In this paper, physical and mechanical properties of PLA-b-PEG-b-PLA are studied during in vitro degradation. The degradation process leads to a mass loss, a decrease of number average molecular weight and an increase of dispersity index. Mechanical experiments are made in a specific experimental set-up designed to create an environment close to in vivo conditions. The viscoelastic behaviour of the material is studied during the degradation. Finally, the mechanical behaviour is modelled with a linear viscoelastic model. A degradation variable is defined and included in the model to describe the hydrolytic degradation. This variable is linked to physical parameters of the macromolecular polymer network. The model allows us to describe weak deformations but become less accurate for larger deformations. The abilities and limits of the model are discussed. Copyright © 2016 Elsevier Ltd. All rights reserved.

  3. Influence of preparation conditions of hollow titania–nickel composite spheres on their catalytic activity for hydrolytic dehydrogenation of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Umegaki, Tetsuo, E-mail: umegaki.tetsuo@nihon-u.ac.jp [Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Ohashi, Takato [Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Xu, Qiang [National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Kojima, Yoshiyuki [Department of Materials and Applied Chemistry, College of Science and Technology, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan)

    2014-04-01

    Highlights: • We study influence of preparation conditions on activity of hollow titania–nickel composite spheres. • The activity for hydrolytic dehydrogenation of NH{sub 3}BH{sub 3} increases with increase of Ti + Ni content. • The activity depends on the amount of PS residue in the hollow spheres. - Abstract: The present work reports influence of preparation conditions of hollow titania–nickel composite spheres on their morphology and catalytic activity for hydrolytic dehydrogenation of ammonia borane (NH{sub 3}BH{sub 3}). The as-prepared hollow titania–nickel composite spheres were characterized by transmission electron microscopy (TEM). Catalytic activities of the hollow spheres for hydrolytic dehydrogenation of aqueous NaBH{sub 4}/NH{sub 3}BH{sub 3} solution improve with the decrease of Ti + Ni content. From the results of FTIR spectra and elemental analysis, the amount of residual polystyrene (PS) templates is able to be reduced by increasing aging time for the preparation, and the catalytic activity of the hollow spheres increases when the amount of residual PS templates decreases. The carbon content in the hollow spheres prepared with aging time = 24 h is 17.3 wt.%, and the evolution of 62 mL hydrogen is finished in about 22 min in the presence of the hollow spheres from aqueous NaBH{sub 4}/NH{sub 3}BH{sub 3} solution. The molar ratio of the hydrolytically generated hydrogen to the initial NH{sub 3}BH{sub 3} in the presence of the hollow spheres is 2.7.

  4. Hydrolytic Degradation and Mechanical Stability of Poly(ε-Caprolactone)/Reduced Graphene Oxide Membranes as Scaffolds for In Vitro Neural Tissue Regeneration.

    Science.gov (United States)

    Sánchez-González, Sandra; Diban, Nazely; Urtiaga, Ane

    2018-03-05

    The present work studies the functional behavior of novel poly(ε-caprolactone) (PCL) membranes functionalized with reduced graphene oxide (rGO) nanoplatelets under simulated in vitro culture conditions (phosphate buffer solution (PBS) at 37 °C) during 1 year, in order to elucidate their applicability as scaffolds for in vitro neural regeneration. The morphological, chemical, and DSC results demonstrated that high internal porosity of the membranes facilitated water permeation and procured an accelerated hydrolytic degradation throughout the bulk pathway. Therefore, similar molecular weight reduction, from 80 kDa to 33 kDa for the control PCL, and to 27 kDa for PCL/rGO membranes, at the end of the study, was observed. After 1 year of hydrolytic degradation, though monomers coming from the hydrolytic cleavage of PCL diffused towards the PBS medium, the pH was barely affected, and the rGO nanoplatelets mainly remained in the membranes which envisaged low cytotoxic effect. On the other hand, the presence of rGO nanomaterials accelerated the loss of mechanical stability of the membranes. However, it is envisioned that the gradual degradation of the PCL/rGO membranes could facilitate cells infiltration, interconnectivity, and tissue formation.

  5. Chimeric cellulase matrix for investigating intramolecular synergism between non-hydrolytic disruptive functions of carbohydrate-binding modules and catalytic hydrolysis.

    Science.gov (United States)

    Wang, Yuguo; Tang, Rentao; Tao, Jin; Wang, Xiaonan; Zheng, Baisong; Feng, Yan

    2012-08-24

    The conversion of renewable cellulosic biomass is of considerable interest for the production of biofuels and materials. The bottleneck in the efficient conversion is the compactness and resistance of crystalline cellulose. Carbohydrate-binding modules (CBMs), which disrupt crystalline cellulose via non-hydrolytic mechanisms, are expected to overcome this bottleneck. However, the lack of convenient methods for quantitative analysis of the disruptive functions of CBMs have hindered systematic studies and molecular modifications. Here we established a practical and systematic platform for quantifying and comparing the non-hydrolytic disruptive activities of CBMs via the synergism of CBMs and a catalytic module within designed chimeric cellulase molecules. Bioinformatics and computational biology were also used to provide a deeper understanding. A convenient vector was constructed to serve as a cellulase matrix into which heterologous CBM sequences can be easily inserted. The resulting chimeric cellulases were suitable for studying disruptive functions, and their activities quantitatively reflected the disruptive functions of CBMs on crystalline cellulose. In addition, this cellulase matrix can be used to construct novel chimeric cellulases with high hydrolytic activities toward crystalline cellulose.

  6. Chimeric Cellulase Matrix for Investigating Intramolecular Synergism between Non-hydrolytic Disruptive Functions of Carbohydrate-binding Modules and Catalytic Hydrolysis*

    Science.gov (United States)

    Wang, Yuguo; Tang, Rentao; Tao, Jin; Wang, Xiaonan; Zheng, Baisong; Feng, Yan

    2012-01-01

    The conversion of renewable cellulosic biomass is of considerable interest for the production of biofuels and materials. The bottleneck in the efficient conversion is the compactness and resistance of crystalline cellulose. Carbohydrate-binding modules (CBMs), which disrupt crystalline cellulose via non-hydrolytic mechanisms, are expected to overcome this bottleneck. However, the lack of convenient methods for quantitative analysis of the disruptive functions of CBMs have hindered systematic studies and molecular modifications. Here we established a practical and systematic platform for quantifying and comparing the non-hydrolytic disruptive activities of CBMs via the synergism of CBMs and a catalytic module within designed chimeric cellulase molecules. Bioinformatics and computational biology were also used to provide a deeper understanding. A convenient vector was constructed to serve as a cellulase matrix into which heterologous CBM sequences can be easily inserted. The resulting chimeric cellulases were suitable for studying disruptive functions, and their activities quantitatively reflected the disruptive functions of CBMs on crystalline cellulose. In addition, this cellulase matrix can be used to construct novel chimeric cellulases with high hydrolytic activities toward crystalline cellulose. PMID:22778256

  7. Hydrolytic and radiolytic degradation of TBP in TBP.30% V/V-dodecane/UO2(NO3)2.HNO3.H2O systems

    International Nuclear Information System (INIS)

    Barreta, L.G.

    1980-01-01

    The hydrolytic and radiolytic degradation of TBP is investigated in systems of TBP 30% V/V-dodecane/H 2 O . HNO 3 . UO 2 (NO 3 ) 2 by gas chromatographic determination of HDBP. No direct relation between the concentration of HDBP formed and the quantity of HNO 3 extracted by the organic phase is observed in the studies of hydrolysis of TBP. The HDBP concentration is seen to increase non-linearly with the concentration of HNO 3 extracted by the organic phase. Radiolytic studies show that for doses greater than 1 Wh/l, the concentration of HDBP formed increases with the dose absorbed by the system. Whith doses smaller than 1 Wh/l and acid concentration greater than 2 M, two distinct patterns of behavior are observed. The concentration of HDBP as a function of the radiation dose absorbed by the system presents a minimum for uranyl nitrate concentrations smaller than 0.9 M; for uranyl nitrate concentrations greater than 1.3 M the concentration of radiolytic HDBP cannot be calculated because the concentration of the hydrolytic HDBP determined is greater than the sum of the experimental concentrations of hydrolytic and radiolytic HDBP. It is known that the dose absorbed by the process solutions during the reprocessing of light water reactor fuel elements is smaller than one Wh/l. Thus, dose rates between zero and one Wh/l should be studied for this system. (Author) [pt

  8. Alternative kinetic energy metrics for Lagrangian systems

    Science.gov (United States)

    Sarlet, W.; Prince, G.

    2010-11-01

    We examine Lagrangian systems on \\ {R}^n with standard kinetic energy terms for the possibility of additional, alternative Lagrangians with kinetic energy metrics different to the Euclidean one. Using the techniques of the inverse problem in the calculus of variations we find necessary and sufficient conditions for the existence of such Lagrangians. We illustrate the problem in two and three dimensions with quadratic and cubic potentials. As an aside we show that the well-known anomalous Lagrangians for the Coulomb problem can be removed by switching on a magnetic field, providing an appealing resolution of the ambiguous quantizations of the hydrogen atom.

  9. Gap Resolution

    Energy Technology Data Exchange (ETDEWEB)

    2017-04-25

    Gap Resolution is a software package that was developed to improve Newbler genome assemblies by automating the closure of sequence gaps caused by repetitive regions in the DNA. This is done by performing the follow steps:1) Identify and distribute the data for each gap in sub-projects. 2) Assemble the data associated with each sub-project using a secondary assembler, such as Newbler or PGA. 3) Determine if any gaps are closed after reassembly, and either design fakes (consensus of closed gap) for those that closed or lab experiments for those that require additional data. The software requires as input a genome assembly produce by the Newbler assembler provided by Roche and 454 data containing paired-end reads.

  10. Principles of chemical kinetics

    CERN Document Server

    House, James E

    2007-01-01

    James House's revised Principles of Chemical Kinetics provides a clear and logical description of chemical kinetics in a manner unlike any other book of its kind. Clearly written with detailed derivations, the text allows students to move rapidly from theoretical concepts of rates of reaction to concrete applications. Unlike other texts, House presents a balanced treatment of kinetic reactions in gas, solution, and solid states. The entire text has been revised and includes many new sections and an additional chapter on applications of kinetics. The topics covered include quantitative rela

  11. Introduction to chemical kinetics

    CERN Document Server

    Soustelle, Michel

    2013-01-01

    This book is a progressive presentation of kinetics of the chemical reactions. It provides complete coverage of the domain of chemical kinetics, which is necessary for the various future users in the fields of Chemistry, Physical Chemistry, Materials Science, Chemical Engineering, Macromolecular Chemistry and Combustion. It will help them to understand the most sophisticated knowledge of their future job area. Over 15 chapters, this book present the fundamentals of chemical kinetics, its relations with reaction mechanisms and kinetic properties. Two chapters are then devoted to experimental re

  12. Chronic impacts of oxytetracycline on mesophilic anaerobic digestion of excess sludge: Inhibition of hydrolytic acidification and enrichment of antibiotic resistome.

    Science.gov (United States)

    Tian, Zhe; Zhang, Yu; Yang, Min

    2018-07-01

    We evaluated the chronic impact of oxytetracycline (OTC) on performance and antibiotic resistance development during the mesophilic anaerobic digestion (AD) of antibiotic-containing biomass. Mesophilic AD was conducted in a completely stirred tank reactor by constantly feeding municipal excess sludge spiked with increasing concentrations of OTC (0-1000 mg L -1 ) under a solid retention time of 20 days over a period of 265 days. Results showed that methane generation of mesophilic AD was inhibited when the OTC concentration in digested sludge was increased to around 18,000 mg kg -1 (OTC dose, 1000 mg L -1 ), due to the inhibition of fermenting and acidogenic bacteria. Metagenomic sequencing and high-throughput quantitative PCR analysis demonstrated that tetracycline resistance genes were the most dominant type (38.47-43.76%) in the resistome, with tetG, tetX, tetM, tetR, tetQ, tetO, and tetL as the dominant resistant subtypes throughout the whole experimental period. The relative abundance of these tet genes increased from 2.10 × 10 -1 before spiking OTC (OTC concentration in digested sludge, 8.97 mg kg -1 ) to 2.83 × 10 -1 (p resistome variation were 29.35% and 21.51%, respectively. Thus, considering the inhibition of hydrolytic acidification and enrichment of antibiotic resistome, mesophilic AD is not suggested to directly treat the biomass containing OTC concentration higher than 200 mg L -1 . Copyright © 2018 Elsevier Ltd. All rights reserved.

  13. Studies on the effect of virtual crosslinking on the hydrolytic stability of novel aliphatic polyurethane ureas for blood contact applications.

    Science.gov (United States)

    Thomas, V; Jayabalan, M

    2001-07-01

    The effect of virtual crosslinking on the hydrolytic stability of completely aliphatic novel poly(urethane ureas), HFL9-PU1 (hard-segment content 57.5%) and HFL13-PU2 (hard-segment content 67.9%) based on 4,4'-methylene bis(cyclohexyl isocyanate) (H(12)MDI)-hydroxy-terminated polybutadiene-1,6-hexamethylene diamine, was studied. Fourier transform infrared-attenuated total reflectance and wide-angle X-ray diffraction studies revealed hydrogen-bonding interaction and microphase separation and formation of crystallites by short- and long-range ordering in hard-segment domains. Three-dimensional networks from hydrogen bonding in the present polymers lead to virtually crosslinking and insolubility. These polymers were noncytotoxic to L929 fibroblast cells. The hemolytic potential is below the accepted limit. The studies on in vitro biostability in Ringer's solution, phosphate buffered saline, and papain enzyme revealed no weight loss. The infrared spectral studies revealed changes in the surface, especially on HFL9-PU1 aged in Ringer's solution and phosphate buffered saline, and no changes when aged in papain. The marginal changes noticed in tensile properties were attributed to the changes in degree of hydrogen bonding and associated rearrangement of molecular structure in the bulk. The results revealed that the lesser the crosslinking in virgin polymer, the higher the crosslinking in aged polymer and vice versa. Increased crosslinking during aging provided increased tensile properties in the aged polymer over the virgin polymer and vice versa. For comparison, an aliphatic polyetherurethane urea (HFL16-PU3) was also synthesized using poly(oxy tetra methylene glycol) in addition to the above reactants. Though both HFL9-PU1 and HFL16-PU3 contained the same hard-segment content, the aged sample of the latter showed decreased tensile properties with increased crosslinking during aging in contrast to the former. This was attributed to less microphase separation in the

  14. THE COORDINATION COMPOUNDS OF COBALT (II, III WITH DITHIOCARBAMIC ACID DERIVATIVES — MODIFICATORS OF HYDROLYTIC ENZYMES ACTIVITY

    Directory of Open Access Journals (Sweden)

    L. D. Varbanets

    2013-02-01

    Full Text Available Chloride, bromide and isothiocyanate complexes of cobalt(II with N-substituted thiocarbamoyl-N?-pentamethylenesulfenamides (1–(12, and also complexes of cobalt(II, Ш with derivatives of morpholine-4-carbodithioic acid (13–(18 have been used as modificators of enzymes of hydrolytic action — Bacillus thurin-giensis ІМВ В-7324 peptidases, Bacillus subtilis 147 and Aspergillus flavus var. oryzae 80428 amylases, Eupenicillium erubescens 248 and Cryptococcus albidus 1001 rhamnosidases. It was shown that cobalt (II, Ш compounds influence differently on the activity of enzymes tested, exerted both inhibitory and stimulatory action. It gives a possibility to expect that manifestation of activity by complex molecule depends on ligand and anion presence — Cl–, Br– or NCS–. The high activating action of cobalt(II complexes with N-substituted thiocarbamoyl-N?-pentamethylenesulphenamides (1–(12 on elastase and fibrinolytic activity of peptidases compared to tris(4-morpholinecarbodithioatocobalt(ІІІ (14 and products of its interaction with halogens (15–(17, causes inhibitory effect that is probably due to presence of a weekly S–N link, which is easy subjected to homolytic breaking. The studies of influences of cobalt(II complexes on activity of C. аlbidus and E. еrubescens ?-Lrhamnosidases showed, that majority of compounds inhibits of its activity, at that the most inhibitory effect exerts to C. аlbidus enzyme.To sum up, it is possible to state that character of influence of cobalt(II complexes with N-substituted thiocarbamoyl-N?-pentamethylenesulphenamides, and also cobalt(II, Ш complexes with derivatives of morpholine-4-carbodithioic acid varies depending on both strain producer and enzyme tested. The difference in complex effects on enzymes tested are due to peculiarities of building and functional groups of their active centers, which are also responsible for binding with modificators.

  15. Kinetic equation solution by inverse kinetic method

    International Nuclear Information System (INIS)

    Salas, G.

    1983-01-01

    We propose a computer program (CAMU) which permits to solve the inverse kinetic equation. The CAMU code is written in HPL language for a HP 982 A microcomputer with a peripheral interface HP 9876 A ''thermal graphic printer''. The CAMU code solves the inverse kinetic equation by taking as data entry the output of the ionization chambers and integrating the equation with the help of the Simpson method. With this program we calculate the evolution of the reactivity in time for a given disturbance

  16. Kinetics in radiation chemistry

    International Nuclear Information System (INIS)

    Hummel, A.

    1987-01-01

    In this chapter the authors first briefly review the kinetics of first- and second-order processes for continuous and pulsed irradiation, without taking the effects of nonhomogeneous formation of the species into consideration. They also discuss diffusion controlled reactions under conditions where interactions of more than two particles can be neglected, first the kinetics of the diffusion-controlled reaction of randomly generated species (homogeneous reaction) and then that of isolated pairs of reactants. The latter is often called geminate kinetics when dealing with pairs of oppositely charged species; they shall use this term for the kinetics of isolated pairs in general. In the last section they discuss briefly the kinetics of groups of more than two reactants

  17. Non-kinetic capabilities: complementing the kinetic prevalence to targeting

    OpenAIRE

    Ducheine, P.

    2014-01-01

    Targeting is used in military doctrine to describe a military operational way, using (military) means to influence a target (or addressee) in order to achieve designated political and/or military goals. The four factors italicized are used to analyse non-kinetic targeting, complementing our knowledge and understanding of the kinetic prevalence. Paradoxically, non-kinetic targeting is not recognized as a separate concept: kinetic and non-kinetic are intertwined facets of targeting. Kinetic tar...

  18. Kinetic Profiles in NSTX Plasmas

    International Nuclear Information System (INIS)

    Bell, R.E.; LeBlanc, B.P.; Bourdelle, C.; Ernst, D.R.; Fredrickson, E.D.; Gates, D.A.; Hosea, J.C.; Johnson, D.W.; Kaye, S.M.; Maingi, R.; Medley, S.; Menard, J.E.; Mueller, D.; Ono, M.; Paoletti, F.; Peng, M.; Sabbagh, S.A.; Stutman, D.; Swain, D.W.; Synakowski, E.J.; Wilson, J.R.

    2001-01-01

    The National Spherical Torus Experiment (NSTX) is a low aspect ratio (R/a approximately 1.3) device with auxiliary heating from neutral-beam injection (NBI) and high-harmonic fast-wave heating (HHFW). Typical NSTX parameters are R(subscript ''0'') = 85 cm, a = 67 cm, I(subscript ''p'') = 0.7-1.4 MA, B(subscript ''phi'') = 0.25-0.45 T. Three co-directed deuterium neutral-beam sources have injected P(subscript ''NB'') less than or equal to 4.7 MW. HHFW plasmas typically have delivered P(subscript ''RF'') less than or equal to 3 MW. Important to the understanding of NSTX confinement are the new kinetic profile diagnostics: a multi-pulse Thomson scattering system (MPTS) and a charge-exchange recombination spectroscopy (CHERS) system. The MPTS diagnostic currently measures electron density and temperature profiles at 30 Hz at ten spatial locations. The CHERS system has recently become available to measure carbon ion temperature and toroidal flow at 17 radial positions spanning the outer half of the minor radius with 20 msec time resolution during NBI. Experiments conducted during the last year have produced a wide range of kinetic profiles in NSTX. Some interesting examples are presented below

  19. Enzymatic kinetic resolution of Morita-Baylis-Hillman acetates

    CSIR Research Space (South Africa)

    Juma, WP

    2017-09-01

    Full Text Available voltage of 15 V. The enzymes 240 used were purchased from Sigma–Aldrich, Enzymes SA or Amano, or were gifts from Novozymes. Enzyme reactions were monitored using chiral HPLC on a Dionex Ultimate 3000 instrument equipped with a photodiode array detector... layer chro- matography) on aluminium-backed Merck silica gel 60 F254 plates. Separation of compounds by column chromatography was per- formed on normal silica gel (particle size 063–0.200 mm) or flash silica gel (particle size 0.040–0.063) purchased from...

  20. Preparation of enantiopure epoxides by biocatalytic kinetic resolution

    NARCIS (Netherlands)

    Weijers, C.A.G.M.

    2001-01-01

    Molecular chirality is of great importance for many processes in biological systems. Examples are interactions with enzymes and receptor systems for hormones, sensory recognition and drug metabolism. Activation of biological activity when initiated by interaction with

  1. Influence of pH on Morphology and Structure during Hydrolytic Degradation of the Segmented GL-b-[GL-co-TMC-co-CL]-b-GL Copolymer

    Directory of Open Access Journals (Sweden)

    Yolanda Márquez

    2015-09-01

    Full Text Available Hydrolytic degradation in media having a continuous variation of pH from 2 to 12 was studied for a copolymer having two polyglycolide hard blocks and a middle soft segment constituted by glycolide, trimethylene carbonate, and ɛ-caprolactone units. The last units were susceptible to cross-linking reactions by γ irradiation that led to an increase of the molecular weight of the sample. Nevertheless, the susceptibility to hydrolytic degradation was enhanced with respect to non-irradiated samples and consequently such samples were selected to analyze the degradation process through weight loss measurements and the evaluation of changes on molecular weight, morphology, and SAXS patterns. Results reflected the different hydrolytic mechanisms that took place in acid and basic media and the different solubilization of the degradation products. Thus, degradation was faster and solubilization higher in the basic media. In this case, fibers showed a high surface erosion and the formation of both longitudinal and deep circumferential cracks that contrasted with the peeling process detected at intermediate pHs (from 6 to 8 and the absence of longitudinal cracks at low pHs. SAXS measurements indicated that degradation was initiated through the hydrolysis of the irregular molecular folds placed on the amorphous interlamellar domains but also affected lamellar crystals at the last stages. Subsequent heating processes performed with degraded samples were fundamental to reveal the changes in microstructure that occurred during degradation and even the initial lamellar arrangement. In particular, the presence of interfibrillar domains and the disposition of lamellar domains at different levels along the fiber axis for a determined cross-section were evidenced.

  2. Kinetics of phase transformations

    International Nuclear Information System (INIS)

    Thompson, M.O.; Aziz, M.J.; Stephenson, G.B.

    1992-01-01

    This volume contains papers presented at the Materials Research Society symposium on Kinetics of Phase Transformations held in Boston, Massachusetts from November 26-29, 1990. The symposium provided a forum for research results in an exceptionally broad and interdisciplinary field. Presentations covered nearly every major class of transformations including solid-solid, liquid-solid, transport phenomena and kinetics modeling. Papers involving amorphous Si, a dominant topic at the symposium, are collected in the first section followed by sections on four major areas of transformation kinetics. The symposium opened with joint sessions on ion and electron beam induced transformations in conjunction with the Surface Chemistry and Beam-Solid Interactions: symposium. Subsequent sessions focused on the areas of ordering and nonlinear diffusion kinetics, solid state reactions and amorphization, kinetics and defects of amorphous silicon, and kinetics of melting and solidification. Seven internationally recognized invited speakers reviewed many of the important problems and recent results in these areas, including defects in amorphous Si, crystal to glass transformations, ordering kinetics, solid-state amorphization, computer modeling, and liquid/solid transformations

  3. Solid phase microextraction as a reliable alternative to conventional extraction techniques to evaluate the pattern of hydrolytically released components in Vitis vinifera L. grapes.

    Science.gov (United States)

    Perestrelo, Rosa; Caldeira, Michael; Câmara, José S

    2012-06-15

    In present research, headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry (GC-qMS), was evaluated as a reliable and improved alternative to the commonly used liquid-liquid extraction (LLE) technique for the establishment of the pattern of hydrolytically released components of 7 Vitis vinifera L. grape varieties, commonly used to produce the world-famous Madeira wine. Since there is no data available on their glycosidic fractions, at a first step, two hydrolyse procedures, acid and enzymatic, were carried out using Boal grapes as matrix. Several parameters susceptible of influencing the hydrolytic process were studied. The best results, expressed as GC peak area, number of identified components and reproducibility, were obtained using ProZym M with b-glucosidase activity at 35°C for 42h. For the extraction of hydrolytically released components, HS-SPME technique was evaluated as a reliable and improved alternative to the conventional extraction technique, LLE (ethyl acetate). HS-SPME using DVB/CAR/PDMS as coating fiber displayed an extraction capacity two fold higher than LLE (ethyl acetate). The hydrolyzed fraction was mainly characterized by the occurrence of aliphatic and aromatic alcohols, followed by acids, esters, carbonyl compounds, terpenoids, and volatile phenols. Concerning to terpenoids its contribution to the total hydrolyzed fraction is highest for Malvasia Cândida (23%) and Malvasia Roxa (13%), and their presence according previous studies, even at low concentration, is important from a sensorial point of view (can impart floral notes to the wines), due to their low odor threshold (μg/L). According to the obtained data by principal component analysis (PCA), the sensorial properties of Madeira wines produced by Malvasia Cândida and Malvasia Roxa could be improved by hydrolysis procedure, since their hydrolyzed fraction is mainly characterized by terpenoids (e.g. linalool, geraniol) which are responsible

  4. Irreversible processes kinetic theory

    CERN Document Server

    Brush, Stephen G

    2013-01-01

    Kinetic Theory, Volume 2: Irreversible Processes deals with the kinetic theory of gases and the irreversible processes they undergo. It includes the two papers by James Clerk Maxwell and Ludwig Boltzmann in which the basic equations for transport processes in gases are formulated, together with the first derivation of Boltzmann's ""H-theorem"" and a discussion of this theorem, along with the problem of irreversibility.Comprised of 10 chapters, this volume begins with an introduction to the fundamental nature of heat and of gases, along with Boltzmann's work on the kinetic theory of gases and s

  5. SHORT COMMUNICATION CATALYTIC KINETIC ...

    African Journals Online (AJOL)

    IV) catalyzes the discoloring reaction of DBS-arsenazo oxidized by potassium bromate, a new catalytic kinetic spectrophotometric method for the determination of trace titanium (IV) was developed. The linear range of the determination of ...

  6. Pre-steady-state Kinetics for Hydrolysis of Insoluble Cellulose by Cellobiohydrolase Cel7A

    DEFF Research Database (Denmark)

    Cruys-Bagger, Nicolaj; Olsen, Jens Elmerdahl; Præstgaard, Eigil

    2012-01-01

    The transient kinetic behavior of enzyme reactions prior to the establishment of steady state is a major source of mechanistic information, yet this approach has not been utilized for cellulases acting on their natural substrate, insoluble cellulose. Here, we elucidate the pre-steady-state regime...... for the exo-acting cellulase Cel7A using amperometric biosensors and an explicit model for processive hydrolysis of cellulose. This analysis allows the identification of a pseudo-steady-state period and quantification of a processivity number as well as rate constants for the formation of a threaded enzyme...... to unveil fundamental reasons for the distinctive variability in hydrolytic activity found in different cellulase-substrate systems....

  7. Curcumin modulation of Na,K-ATPase: phosphoenzyme accumulation, decreased K+ occlusion, and inhibition of hydrolytic activity

    DEFF Research Database (Denmark)

    Mahmmoud, Yasser Ahmed

    2005-01-01

    Curcumin, the major constitute of tumeric, is an important nutraceutical that has been shown to be useful in the treatment of many diseases. As an inhibitor of the sarcoplasmic reticulum Ca2+-ATPase, curcumin was shown to correct cystic fibrosis (CF) defects in some model systems, whereas others...... have reported no or little effects on CF after curcumin treatment, suggesting that curcumin effect is not due to simple inhibition of the Ca2+-ATPase. We tested the hypothesis that curcumin may modulate other members of the P2-type ATPase superfamily by studying the effects of curcumin on the activity...... and kinetic properties of the Na,K-ATPase. Curcumin treatment inhibited Na,K-ATPase activity in a dose-dependent manner (K0.514.6 M). Curcumin decreased the apparent affinity of Na,K-ATPase for K+ and increased it for Na+ and ATP. Kinetic analyses indicated that curcumin induces a three-fold reduction...

  8. 2-O-α-D-glucosylglycerol phosphorylase from Bacillus selenitireducens MLS10 possessing hydrolytic activity on β-D-glucose 1-phosphate.

    Directory of Open Access Journals (Sweden)

    Takanori Nihira

    Full Text Available The glycoside hydrolase family (GH 65 is a family of inverting phosphorylases that act on α-glucosides. A GH65 protein (Bsel_2816 from Bacillus selenitireducens MLS10 exhibited inorganic phosphate (Pi-dependent hydrolysis of kojibiose at the rate of 0.43 s(-1. No carbohydrate acted as acceptor for the reverse phosphorolysis using β-D-glucose 1-phosphate (βGlc1P as donor. During the search for a suitable acceptor, we found that Bsel_2816 possessed hydrolytic activity on βGlc1P with a k cat of 2.8 s(-1; moreover, such significant hydrolytic activity on sugar 1-phosphate had not been reported for any inverting phosphorylase. The H2 (18O incorporation experiment and the anomeric analysis during the hydrolysis of βGlc1P revealed that the hydrolysis was due to the glucosyl-transferring reaction to a water molecule and not a phosphatase-type reaction. Glycerol was found to be the best acceptor to generate 2-O-α-D-glucosylglycerol (GG at the rate of 180 s(-1. Bsel_2816 phosphorolyzed GG through sequential Bi-Bi mechanism with a k cat of 95 s(-1. We propose 2-O-α-D-glucopyranosylglycerol: phosphate β-D-glucosyltransferase as the systematic name and 2-O-α-D-glucosylglycerol phosphorylase as the short name for Bsel_2816. This is the first report describing a phosphorylase that utilizes polyols, and not carbohydrates, as suitable acceptor substrates.

  9. Effect of Chain-Extenders on the Properties and Hydrolytic Degradation Behavior of the Poly(lactide/ Poly(butylene adipate-co-terephthalate Blends

    Directory of Open Access Journals (Sweden)

    Mingqing Chen

    2013-10-01

    Full Text Available Biodegradable poly(lactide/poly(butylene adipate-co-terephthalate (PLA/PBAT blends were prepared by reactive blending in the presence of chain-extenders. Two chain-extenders with multi-epoxy groups were studied. The effect of chain-extenders on the morphology, mechanical properties, thermal behavior, and hydrolytic degradation of the blends was investigated. The compatibility between the PLA and PBAT was significantly improved by in situ formation of PLA-co-PBAT copolymers in the presence of the chain-extenders, results in an enhanced ductility of the blends, e.g., the elongation at break was increased to 500% without any decrease in the tensile strength. The differential scanning calorimeter (DSC results reveal that cold crystallization of PLA was enhanced due to heterogeneous nucleation effect of the in situ compatibilized PBAT domains. As known before, PLA is sensitive to hydrolysis and in the presence of PBAT and the chain-extenders, the hydrolytic degradation of the blend was evident. A three-stage hydrolysis mechanism for the system is proposed based on a study of weight loss and molecular weight reduction of the samples and the pH variation of the degradation medium.

  10. Effect of the crude extract of Eugenia uniflora in morphogenesis and secretion of hydrolytic enzymes in Candida albicans from the oral cavity of kidney transplant recipients.

    Science.gov (United States)

    Silva-Rocha, Walicyranison Plinio; de Brito Lemos, Vitor Luiz; Ferreira, Magda Rhayanny Assunção; Soares, Luiz Alberto Lira; Svidzisnki, Terezinha Inês Estivalet; Milan, Eveline Pipolo; Chaves, Guilherme Maranhão

    2015-02-05

    Candida albicans is a diploid yeast that in some circumstances may cause oral or oropharyngeal infections. Yeasts virulence factors contribute for both the maintenance of colonizing strains in addition to damage and cause tissue invasion, thus the establishment of infection occurs. The limited arsenal of antifungal drugs for the treatment of candidiasis turn the investigation of natural products mandatory for the discovery of new targets for antifungal drug development. Therefore, tropical countries emerge as important providers of natural products with potential antimicrobial activity. This study aimed to investigate morphogenesis and secretion of hydrolytic enzymes (phospholipase and proteinase) in the presence of the CE of Eugenia uniflora. The isolates were tested for their ability to form hyphae in both solid and liquid media under three different conditions: YPD + 20% FBS, Spider medium and GlcNac and the ability to secrete phospholipase and proteinase in the presence of 2000 μg/mL of E. uniflora. The CE of E. uniflora inhibited hypha formation in both liquid and solid media tested. It also impaired hydrolytic enzymes production. This was the first study to describe the interaction of a natural product with the full expression of three different factors in C. albicans. E. uniflora may be an alternative therapeutic for oral candidiasis in the future.

  11. Stereo-selective hydrolytic reaction of toxic compounds by enzyme immobilized on porous ceramics; Takoshitsu ceramics kotaika koso ni yoru dokusei kagobutsu no rittai sentakuteki kasui bunkai hanno

    Energy Technology Data Exchange (ETDEWEB)

    Kato, K.; Saito, T. [National Industrial Research Institute of Nagoya, Nagoya (Japan)

    2000-08-25

    Experiment was made on stereo-selective hydrolytic reaction of trifluoroethyl ester of ketoprophene by various kinds of lipase. In addition, study was made on the stability of lipase simply immobilized on porous ceramics under the existence of organic solvent. In the experiment, the hydrolytic activity of 8 kinds of lipase was studied for ketoprophene monochloroethyl ester (1a) and trifluoroethyl ester (1b). The experiment result showed that lipase M originating in mold (Mucor Javanicus) shows a high reactivity and stereo-selectivity for the compound (1a). The lipase immobilized on porous ceramics was easily obtained by a very simple method composed of only throwing carriers into enzyme suspension, agitation and refrigerated drying. The lipase immobilized on porous ceramics 'Toyonite 200-A' synthesized from kaolinite retained the residual activity of nearly 50%, original selectivity and considerable stability after 5 times of repetitive uses. This study result is useful for bio- reactors and bio-sensors for synthesis or decomposition of compounds. (NEDO)

  12. Study of extraction kinetics of lanthanides(III) and actinides(III) nitrates by the molecule N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide

    International Nuclear Information System (INIS)

    Daldon, M.

    1999-01-01

    The kinetics of extraction of lanthanides (III) and actinides (III) nitrates by the molecule N, N'-dimethyl - N, N'-dibutyl tetra-decyl malonamide has been investigated. This study was realised with a new constant interfacial-area-stirred cell. During the qualification step of the device it appears that the reduction of the device can lead to hydrolytic perturbations. The main conclusions are: - after the determination of conditions which provide kinetics regime (diffusion of species neglectable), partial orders of the kinetics law have been obtained and lead to the establishment of the law J = k [Nd 3+ ] [NO 3 - ] 3 [diamide] 1 , - interfacial tension measurements and kinetics study in presence of surface-active compounds proved that the chemical limiting reaction for Nd(III) is interfacial, - the results allow to propose an adsorption-desorption reaction mechanism, - a comprehensive study of the extraction kinetics of the lanthanides(III) series and also Am(III) and Cm(III) nitrates has been realised. The lighter lanthanides (La, Ce and Pr) exhibit higher kinetics rate of extraction than the others, which differs from the tendency observed with distribution coefficients which exhibit tetrad effect. The kinetics rate of extraction of Am(III) and Cm(III) is closed to the value of Eu(III). (author)

  13. Relativistic Chiral Kinetic Theory

    International Nuclear Information System (INIS)

    Stephanov, Mikhail

    2016-01-01

    This very brief review of the recent progress in chiral kinetic theory is based on the results of Refs. [J.-Y. Chen, D. T. Son, M. A. Stephanov, H.-U. Yee, Y. Yin, Lorentz Invariance in Chiral Kinetic Theory, Phys. Rev. Lett. 113 (18) (2014) 182302. doi: (10.1103/PhysRevLett.113.182302); J.-Y. Chen, D. T. Son, M. A. Stephanov, Collisions in Chiral Kinetic Theory, Phys. Rev. Lett. 115 (2) (2015) 021601. doi: (10.1103/PhysRevLett.115.021601); M. A. Stephanov, H.-U. Yee, The no-drag frame for anomalous chiral fluid, Phys. Rev. Lett. 116 (12) (2016) 122302. doi: (10.1103/PhysRevLett.116.122302)].

  14. Relativistic Chiral Kinetic Theory

    Energy Technology Data Exchange (ETDEWEB)

    Stephanov, Mikhail

    2016-12-15

    This very brief review of the recent progress in chiral kinetic theory is based on the results of Refs. [J.-Y. Chen, D. T. Son, M. A. Stephanov, H.-U. Yee, Y. Yin, Lorentz Invariance in Chiral Kinetic Theory, Phys. Rev. Lett. 113 (18) (2014) 182302. doi: (10.1103/PhysRevLett.113.182302); J.-Y. Chen, D. T. Son, M. A. Stephanov, Collisions in Chiral Kinetic Theory, Phys. Rev. Lett. 115 (2) (2015) 021601. doi: (10.1103/PhysRevLett.115.021601); M. A. Stephanov, H.-U. Yee, The no-drag frame for anomalous chiral fluid, Phys. Rev. Lett. 116 (12) (2016) 122302. doi: (10.1103/PhysRevLett.116.122302)].

  15. Erbium hydride decomposition kinetics.

    Energy Technology Data Exchange (ETDEWEB)

    Ferrizz, Robert Matthew

    2006-11-01

    Thermal desorption spectroscopy (TDS) is used to study the decomposition kinetics of erbium hydride thin films. The TDS results presented in this report are analyzed quantitatively using Redhead's method to yield kinetic parameters (E{sub A} {approx} 54.2 kcal/mol), which are then utilized to predict hydrogen outgassing in vacuum for a variety of thermal treatments. Interestingly, it was found that the activation energy for desorption can vary by more than 7 kcal/mol (0.30 eV) for seemingly similar samples. In addition, small amounts of less-stable hydrogen were observed for all erbium dihydride films. A detailed explanation of several approaches for analyzing thermal desorption spectra to obtain kinetic information is included as an appendix.

  16. Instrumentation for millisecond-resolution scattering studies

    International Nuclear Information System (INIS)

    Stephenson, G.B.; Ludwig, K.F. Jr.; Jordan-Sweet, J.L.; Brauer, S.; Mainville, J.; Yang, Y.S.; Sutton, M.

    1989-01-01

    Time-resolved x-ray scattering studies of phase transition kinetics have been carried out using the wide-bandpass monochromator and fast linear position-sensitive detector system at the IBM/MIT beamline X-20C at the National Synchrotron Light Source (NSLS). We report here on the instrumentation that has been developed for these studies, and in particular on the methods used to measure, change, and control sample temperature with millisecond resolution

  17. Relativistic Kinetic Theory

    Science.gov (United States)

    Vereshchagin, Gregory V.; Aksenov, Alexey G.

    2017-02-01

    Preface; Acknowledgements; Acronyms and definitions; Introduction; Part I. Theoretical Foundations: 1. Basic concepts; 2. Kinetic equation; 3. Averaging; 4. Conservation laws and equilibrium; 5. Relativistic BBGKY hierarchy; 6. Basic parameters in gases and plasmas; Part II. Numerical Methods: 7. The basics of computational physics; 8. Direct integration of Boltzmann equations; 9. Multidimensional hydrodynamics; Part III. Applications: 10. Wave dispersion in relativistic plasma; 11. Thermalization in relativistic plasma; 12. Kinetics of particles in strong fields; 13. Compton scattering in astrophysics and cosmology; 14. Self-gravitating systems; 15. Neutrinos, gravitational collapse and supernovae; Appendices; Bibliography; Index.

  18. Quantum kinetic theory

    CERN Document Server

    Bonitz, Michael

    2016-01-01

    This book presents quantum kinetic theory in a comprehensive way. The focus is on density operator methods and on non-equilibrium Green functions. The theory allows to rigorously treat nonequilibrium dynamics in quantum many-body systems. Of particular interest are ultrafast processes in plasmas, condensed matter and trapped atoms that are stimulated by rapidly developing experiments with short pulse lasers and free electron lasers. To describe these experiments theoretically, the most powerful approach is given by non-Markovian quantum kinetic equations that are discussed in detail, including computational aspects.

  19. Influence of preparation conditions of hollow silica–nickel composite spheres on their catalytic activity for hydrolytic dehydrogenation of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Umegaki, Tetsuo, E-mail: umegaki.tetsuo@nihon-u.ac.jp [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Seki, Ayano [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan); Xu, Qiang [National Institute of Advanced Industrial Science and Technology (AIST), 1-8-31 Midorigaoka, Ikeda, Osaka 563-8577 (Japan); Kojima, Yoshiyuki [Department of Materials and Applied Chemistry, College of Science and Engineering, Nihon University, 1-8-14, Kanda-Surugadai, Chiyoda-Ku, Tokyo 101-8308 (Japan)

    2014-03-05

    Highlights: • We study influence of preparation conditions on activity of hollow silica–nickel composite spheres. • The activity for hydrolytic dehydrogenation of NH{sub 3}BH{sub 3} increases with increase of Si+Ni content. • The particle size distribution affects the activity and reducibility of active nickel species. • The amount of PS residue in the hollow spheres decreases by treatment of as-prepared sample in toluene. -- Abstract: In this paper, we investigated influence of preparation conditions of hollow silica–nickel composite spheres on their morphology and catalytic activity for hydrolytic dehydrogenation of ammonia borane. In the preparation method of this study, when silica–nickel composite shells were coated on polystyrene templates by the sol–gel method using L(+)-arginine as the promoter for the reaction to form silica–nickel composite shell, the polystyrene templates were dissolved subsequently, even synchronously, in the same medium to form hollow spheres. The as-prepared silica–nickel composite spheres were characterized by transmission electron microscopy and scanning electron microscopy. The effects of Si+Ni content on the morphology were systematically evaluated. All the as-prepared hollow silica–nickel composite spheres have the similar morphology as identified by SEM and TEM measurement. Homogeneity of the hollow silica–nickel composite spheres increases with the increase in the Si+Ni content as shown by the laser diffraction particle size analysis. The catalytic activities of the hollow silica–nickel composite spheres for hydrolytic dehydrogenation of ammonia borane prepared with different Si+Ni contents were compared. The catalytic activity for the hydrogen evolution in the presence of the hollow spheres increases with the increase of Si+Ni content. The results of FTIR spectra of the hollow silica–nickel composite spheres indicate that a certain amount of residual PS templates exists in hollow silica

  20. Development of Conductivity Method as an Alternative to Titration for Hydrolytic Resistance Testing Used for Evaluation of Glass Vials Used in Pharmaceutical Industry.

    Science.gov (United States)

    Fujimori, Kiyoshi; Lee, Hans; Phillips, Joseph; Nashed-Samuel, Yasser

    The European Pharmacopeia surface test to analyze the hydrolytic resistance is a common industrial method to understand and ensure the quality of produced glass vials. Hydrolytic resistance is evaluated by calculating the alkalinity of water extract from autoclaved vials by titration. As an alternative to this titration technique, a conductivity technique was assessed, which directly measures the ions in the water extract. A conductivity meter with a 12 mm diameter electrode was calibrated with a 100 μS/cm conductivity standard and carryover minimized by rinsing the probe in a water beaker per analysis. The limit of quantification at 1 μS/cm was determined as having a signal-to-noise ratio of 3 compared with the water blank. The conductivity method was selective for glass-composing elements (boron, sodium, aluminum, silicon, potassium, and calcium) within the vial extract. Accuracies of spiked conductivity standard within the range of 1 to 100 μS/cm were ±7% and had linearity with coefficient of determination (R 2 ) of ≥0.9999. Intraday precision had a relative standard deviation (RSD) (n = 5) of ≤6% for spiked conductivity standard within the range of 1 to 100 μS/cm. Interday precision had a RSD (n = 4) of ≤6% for 10 vials from three glass vial lots. Conductivity of water extracts from nine sets of seven lots of glass vials had a precise linear relationship [R 2 = 0.9876, RSD = 1% (n = 9)] with titration volumes of the same lots. Conductivity results in μS/cm could be converted to titration volumes in milliliters by a conversion factor of 0.0275. The simplicity, sample stability, and individual vial analysis of the conductivity technique were more advantageous than the current titration technique. The quality of glass vials used as primary containers in the pharmaceutical industry is of concern due to recent observations of glass flake-like delamination, or lamellae, under specific storage conditions. The current European Pharmacopoeia method to assess

  1. Organic matter recycling in a shallow coastal zone (NW Mediterranean): The influence of local and global climatic forcing and organic matter lability on hydrolytic enzyme activity

    Science.gov (United States)

    Misic, Cristina; Harriague, Anabella Covazzi

    2008-12-01

    Seawater and sediment were collected on a monthly basis from a shallow (10.5 m depth) coastal site in the Ligurian Sea (NW Mediterranean) from November 1993 to December 1994 to determine the main environmental forces that influenced the biogeochemical processes and to study the relationships between the availability and lability of the organic matter (OM) and hydrolytic enzymatic activity. The current direction throughout the sampling year was influenced by the climatic conditions, which showed significant correlations with north atlantic oscillation (NAO) index values. The current generally flowed northwards in spring. This could cause significantly lower transparency values than in the summer, when an eastward current probably reduced the allochthonous input of material from the main local watercourse and contributed to turning the conditions from mesotrophic to oligotrophic. Spring and summer were separated by transitional periods more than by the canonical autumn and winter seasons. These transitions were characterised by a reduction in salinity values and by resuspension caused by water column mixing and a current flowing towards the southwest. The significant inverse correlations of the chlorophyll- a and protein concentrations, bacterial abundance and proteolysis of the bottom seawater and transparency showed the direct influence of resuspension on the organic matter dynamics. Moreover, OM trophic quality influenced the bacterial parameters and the enzymatic activities. The glycolytic β glucosidase and chitinase activities and their bacterial cell-specific hydrolytic rates were higher when substrates such as hydrolysable proteins were available, while they decreased when refractory compounds were abundant. The low leucine aminopeptidase: β glucosidase ratio values observed in the water column were presumably related to the potential ease with which microbes obtained protein-derived materials and energy, the protein hydrolysable fraction being estimated at

  2. Oxidative desulfurization: kinetic modelling.

    Science.gov (United States)

    Dhir, S; Uppaluri, R; Purkait, M K

    2009-01-30

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H(2)O(2) over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel.

  3. Oxidative desulfurization: Kinetic modelling

    International Nuclear Information System (INIS)

    Dhir, S.; Uppaluri, R.; Purkait, M.K.

    2009-01-01

    Increasing environmental legislations coupled with enhanced production of petroleum products demand, the deployment of novel technologies to remove organic sulfur efficiently. This work represents the kinetic modeling of ODS using H 2 O 2 over tungsten-containing layered double hydroxide (LDH) using the experimental data provided by Hulea et al. [V. Hulea, A.L. Maciuca, F. Fajula, E. Dumitriu, Catalytic oxidation of thiophenes and thioethers with hydrogen peroxide in the presence of W-containing layered double hydroxides, Appl. Catal. A: Gen. 313 (2) (2006) 200-207]. The kinetic modeling approach in this work initially targets the scope of the generation of a superstructure of micro-kinetic reaction schemes and models assuming Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms. Subsequently, the screening and selection of above models is initially based on profile-based elimination of incompetent schemes followed by non-linear regression search performed using the Levenberg-Marquardt algorithm (LMA) for the chosen models. The above analysis inferred that Eley-Rideal mechanism describes the kinetic behavior of ODS process using tungsten-containing LDH, with adsorption of reactant and intermediate product only taking place on the catalyst surface. Finally, an economic index is presented that scopes the economic aspects of the novel catalytic technology with the parameters obtained during regression analysis to conclude that the cost factor for the catalyst is 0.0062-0.04759 US $ per barrel

  4. Modeling chemical kinetics graphically

    NARCIS (Netherlands)

    Heck, A.

    2012-01-01

    In literature on chemistry education it has often been suggested that students, at high school level and beyond, can benefit in their studies of chemical kinetics from computer supported activities. Use of system dynamics modeling software is one of the suggested quantitative approaches that could

  5. CATALYTIC KINETIC SPECTROPHOTOMETRIC DETERMINATION ...

    African Journals Online (AJOL)

    Preferred Customer

    acetylchlorophosphonazo(CPApA) by hydrogen peroxide in 0.10 M phosphoric acid. A novel catalytic kinetic-spectrophotometric method is proposed for the determination of copper based on this principle. Copper(II) can be determined spectrophotometrically ...

  6. Kinetic energy budget details

    Indian Academy of Sciences (India)

    Abstract. This paper presents the detailed turbulent kinetic energy budget and higher order statistics of flow behind a surface-mounted rib with and without superimposed acoustic excitation. Pattern recognition technique is used to determine the large-scale structure magnitude. It is observed that most of the turbulence ...

  7. Point kinetics modeling

    International Nuclear Information System (INIS)

    Kimpland, R.H.

    1996-01-01

    A normalized form of the point kinetics equations, a prompt jump approximation, and the Nordheim-Fuchs model are used to model nuclear systems. Reactivity feedback mechanisms considered include volumetric expansion, thermal neutron temperature effect, Doppler effect and void formation. A sample problem of an excursion occurring in a plutonium solution accidentally formed in a glovebox is presented

  8. Production of hydrolytic enzymes by Trichoderma isolates with antagonistic activity against Crinipellis perniciosa, the causal agent of witches' broom of cocoa

    Directory of Open Access Journals (Sweden)

    Marco Janice Lisboa De

    2003-01-01

    Full Text Available Two isolates of Trichoderma, which reduce the incidence of witches'broom disease caused in cocoa by Crinipellis perniciosa, were evaluated for their potential to produce hydrolases in liquid medium. Very low or no hydrolytic activity was produced in the absence of any substrate. The activities of chitinase, N-acetylglucosaminidase, beta-1,3-glucanase, total cellulase, endoglucanase, aryl- beta-glucosidase, beta-glucosidase, protease and amylase increased dramatically within 72-120 h of growth in the presence of specific substrates. Except for N-acetylglucosaminidase and beta-glucosidase Trichoderma harzianum isolate 1051 produced the largest amounts of hydrolases. The possible involvement of these enzymes in the antagonistic interaction between Trichoderma and C. perniciosa is discussed.

  9. CuCo2O4 nanoplate film as a low-cost, highly active and durable catalyst towards the hydrolytic dehydrogenation of ammonia borane for hydrogen production

    Science.gov (United States)

    Liu, Quanbing; Zhang, Shengjie; Liao, Jinyun; Feng, Kejun; Zheng, Yuying; Pollet, Bruno G.; Li, Hao

    2017-07-01

    Catalytic dehydrogenation of ammonia borane is one of the most promising routes for the production of clean hydrogen as it is seen as a highly efficient and safe method. However, its large-scale industrial application is either limited by the high cost of the catalyst (usually a noble metal based catalyst) or by the low activity and poor reusability (usually a non-noble metal catalyst). In this study, we have successfully prepared three low-cost CuCo2O4 nanocatalysts, namely: (i) Ti supported CuCo2O4 film made of CuCo2O4 nanoplates, (ii) Ti supported CuCo2O4 film made of CuCo2O4 nanosheets, and (iii) unsupported CuCo2O4 nanoparticles. Among the three catalysts used for the hydrolytic dehydrogeneration of ammonia borane, the CuCo2O4 nanoplate film exhibits the highest catalytic activity with a turnover frequency (TOF) of ∼44.0 molhydrogen min-1 molcat-1. This is one of the largest TOF value for noble-metal-free catalysts ever reported in the literature. Moreover, the CuCo2O4 nanoplate film almost keeps its original catalytic activity after eight cycles, indicative of its high stability and good reusability. Owing to its advantages, the CuCo2O4 nanoplate film can be a promising catalyst for the hydrolytic dehydrogenation of ammonia borane, which may find important applications in the field of hydrogen energy.

  10. A Copper(II)-Paddlewheel Metal-Organic Framework with Exceptional Hydrolytic Stability and Selective Adsorption and Detection Ability of Aniline in Water.

    Science.gov (United States)

    Chen, Ya; Wang, Bin; Wang, Xiaoqing; Xie, Lin-Hua; Li, Jinping; Xie, Yabo; Li, Jian-Rong

    2017-08-16

    Copper(II)-paddlewheel-based metal-organic frameworks (CP-MOFs) represent a unique subclass of MOFs with highly predictable porous structures, facile syntheses, and functional open metal sites. However, the lack of high hydrolytic stability is an obstacle for CP-MOFs in many practical applications. In this work, we report a new CP-MOF, [Cu 4 (tdhb)] (BUT-155), which is constructed from a judiciously designed carboxylate ligand with high coordination connectivity (octatopic), abundant hydrophobic substituents (six methyl groups), and substituent constrained geometry (tetrahedral backbone), tdhb 8- [H 8 tdhb = 3,3',5,5'-tetrakis(3,5-dicarboxyphenyl)-2,2',4,4',6,6'-hexamethylbiphenyl)]. BUT-155 shows high porosity with a Brunauer-Emmett-Teller surface area of 2070 m 2 /g. Quite interestingly, this CP-MOF retains its structural integrity after being treated in water for 10 days at room temperature or in boiling water for 24 h. To the best of our knowledge, BUT-155 represents the first CP-MOF that is demonstrated to retain its structural integrity in boiling water. The high hydrolytic stability of BUT-155 allowed us to carry out adsorption studies of water vapor and aqueous organic pollutants on it. Water-vapor adsorption reveals a sigmoidal isotherm and a high uptake (46.7 wt %), which is highly reversible and regenerable. In addition, because of the availability of soft-acid-type open Cu(II) sites, BUT-155 shows a high performance for selective adsorption of soft-base-type aniline over water or phenol, and a naked-eye detectable color change for the MOF sample accompanies this. The adsorption selectivity and high adsorption capacity of aniline in BUT-155 are also well-interpreted by single-crystal structures of the water- and aniline-included phases of BUT-155.

  11. Evolving transpeptidase and hydrolytic variants of γ-glutamyl transpeptidase from Bacillus licheniformis by targeted mutations of conserved residue Arg109 and their biotechnological relevance.

    Science.gov (United States)

    Bindal, Shruti; Sharma, Sujata; Singh, Tej P; Gupta, Rani

    2017-05-10

    γ-Glutamyl transpeptidase (GGT) catalyzes the transfer of the γ-glutamyl moiety from donor compounds such as l-glutamine (Gln) and glutathione (GSH) to an acceptor. During the biosynthesis of various γ-glutamyl-containing compounds using GGT enzyme, auto-transpeptidation reaction leads to the formation of unwanted byproducts. Therefore, in order to alter the auto-transpeptidase activity of the GGT enzyme, the binding affinity of Gln should be modified. Structural studies of the Bacillus licheniformis GGT (BlGT) complexed with the glutamic acid has shown that glutamic acid has strong ionic interactions through its α-carboxlic group with the guanidine moiety of Arg109. This interaction appears to be an important contributor for the binding affinity of Gln. In view of this, six mutants of Bacillus licheniformis ER15 GGT (BlGGT) viz. Arg109Lys, Arg109Ser, Arg109Met, Arg109Leu, Arg109Glu and Arg109Phe were prepared. As seen from the structure of BlGT, the mutation of Arg109 to Lys109 may reduce the affinity for Gln to some extent, whereas the other mutations are expected to lower the affinity much more. Biophysical characterization and functional studies revealed that Arg109Lys mutant has increased transpeptidation activity and catalytic efficiency than the other mutants. The Arg109Lys mutant showed high conversion rates for l-theanine synthesis as well. Moreover, the Arg109Met mutant showed increased hydrolytic activity as it completely altered the binding of Gln at the active site. Also, the salt stability of the enzyme was significantly improved on replacing Arg109 by Met109 which is required for hydrolytic applications of GGTs in food industries. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Blending of soluble corn fiber with pullulan, sorbitol, or fructose attenuates glycemic and insulinemic responses in the dog and affects hydrolytic digestion in vitro.

    Science.gov (United States)

    de Godoy, M R C; Knapp, B K; Bauer, L L; Swanson, K S; Fahey, G C

    2013-08-01

    The objective of these experiments was to measure in vitro hydrolytic digestion and glycemic and insulinemic responses of select carbohydrate blends, all containing the novel carbohydrate soluble corn fiber (SCF). Two SCF that varied in their method of production were used to formulate the carbohydrate blends. One set of blends contained a SCF that was spray dried (SCFsd) and then blended with different amounts of either pullulan, sorbitol, or fructose. The other set of blends contained a SCF produced using longer evaporation time (SCF) and then blended with different ratios of pullulan, sorbitol, and fructose. Free sugar concentrations found in the individual SCFsd and SCF substrates were low but varied. Spray-dried soluble corn fiber had a reduced free sugar concentration compared with SCF (2.8 vs. 14.2%). Glucose was the main free sugar found in both SCFsd and SCF but at different concentrations (2.7 vs. 12.7%, respectively). The majority of the SCFsd blends were completely hydrolyzed to their monosaccharide components. Glucose accounted for most of the hydrolyzed monosaccharides for SCFsd and all the SCFsd blends. Hydrolyzed monosaccharide concentrations for the SCF:pullulan:sorbitol:fructose blends followed similar trends to the SCFsd blends where greater percentages of fructose and sorbitol resulted in decreased (P sorbitol. Total released monosaccharides were high in SCFsd blends containing either 50% fructose or sorbitol, but the combination resulted in reduced concentrations of glucose released (P sorbitol:fructose blends also had intermediate to high released monosaccharides as a result of in vitro hydrolytic digestion. All SCF blends resulted in decreased glycemic and insulinemic responses compared with the maltodextrin control (P sorbitol in the blends had the greatest impact on glycemic and insulinemic responses, even at concentrations as low as 5% of the blends. Overall, SCF and their blends may prove beneficial as components of low glycemic

  13. Biomass production and secretion of hydrolytic enzymes are influenced by the structural complexity of the nitrogen source in Fusarium oxysporum and Aspergillus nidulans.

    Science.gov (United States)

    da Silva, M C; Bertolini, M C; Ernandes, J R

    2001-01-01

    The structural complexity of the nitrogen sources strongly affects biomass production and secretion of hydrolytic enzymes in filamentous fungi. Fusarium oxysporum and Aspergillus nidulans were grown in media containing glucose or starch, and supplemented with a nitrogen source varying from a single ammonium salt (ammonium sulfate) to free amino acids (casamino acids), peptides (peptone) and protein (gelatin). In glucose, when the initial pH was adjusted to 5.0, for both microorganisms, higher biomass production occurred upon supplementation with a nitrogen source in the peptide form (peptone and gelatin). With a close to neutrality pH, biomass accumulation was lower only in the presence of the ammonium salt. When grown in starch, biomass accumulation and secretion of hydrolytic enzymes (amylolytic and proteolytic) by Fusarium also depended on the nature of the nitrogen supplement and the pH. When the initial pH was adjusted to 5.0, higher growth and higher amylolytic activities were detected in the media supplemented with peptone, gelatin and casamino acids. However, at pH 7.0, higher biomass accumulation and higher amylolytic activities were observed upon supplementation with peptone or gelatin. Ammonium sulfate and casamino acids induced a lower production of biomass, and a different level of amylolytic enzyme secretion: high in ammonium sulfate and low in casamino acids. Secretion of proteolytic activity was always higher in the media supplemented with peptone and gelatin. Aspergillus, when grown in starch, was not as dependent as Fusarium on the nature of nitrogen source or the pH. The results described in this work indicate that the metabolism of fungi is regulated not only by pH, but also by the level of structural complexity of the nitrogen source in correlation to the carbon source.

  14. Investigation of the Fusarium virguliforme Transcriptomes Induced during Infection of Soybean Roots Suggests that Enzymes with Hydrolytic Activities Could Play a Major Role in Root Necrosis.

    Science.gov (United States)

    Sahu, Binod B; Baumbach, Jordan L; Singh, Prashant; Srivastava, Subodh K; Yi, Xiaoping; Bhattacharyya, Madan K

    2017-01-01

    Sudden death syndrome (SDS) is caused by the fungal pathogen, Fusarium virguliforme, and is a major threat to soybean production in North America. There are two major components of this disease: (i) root necrosis and (ii) foliar SDS. Root symptoms consist of root necrosis with vascular discoloration. Foliar SDS is characterized by interveinal chlorosis and leaf necrosis, and in severe cases by flower and pod abscission. A major toxin involved in initiating foliar SDS has been identified. Nothing is known about how root necrosis develops. In order to unravel the mechanisms used by the pathogen to cause root necrosis, the transcriptome of the pathogen in infected soybean root tissues of a susceptible cultivar, 'Essex', was investigated. The transcriptomes of the germinating conidia and mycelia were also examined. Of the 14,845 predicted F. virguliforme genes, we observed that 12,017 (81%) were expressed in germinating conidia and 12,208 (82%) in mycelia and 10,626 (72%) in infected soybean roots. Of the 10,626 genes induced in infected roots, 224 were transcribed only following infection. Expression of several infection-induced genes encoding enzymes with oxidation-reduction properties suggests that degradation of antimicrobial compounds such as the phytoalexin, glyceollin, could be important in early stages of the root tissue infection. Enzymes with hydrolytic and catalytic activities could play an important role in establishing the necrotrophic phase. The expression of a large number of genes encoding enzymes with catalytic and hydrolytic activities during the late infection stages suggests that cell wall degradation could be involved in root necrosis and the establishment of the necrotrophic phase in this pathogen.

  15. Assessment by HPLC of the degradation behavior of acitretin under hydrolytic, oxidative, photolytic and thermal stress conditions

    Directory of Open Access Journals (Sweden)

    Pawan K. Porwal

    2014-12-01

    Full Text Available Acitretin is a photosensitive oral retinoid with very limited data available on its degradation. The official HPLC method for acitretin determination was insufficient to resolve the degradation products generated during stability studies. Therefore, an isocratic RP-HPLC–UV method was developed for the determination of acitretin in the presence of its related impurities and degradation products. Efficient chromatographic separation was achieved on a Thermo beta-basic column C18 (100 mm×4.6 mm, 5 μm with mobile phase containing 0.3% (v/v glacial acetic acid with acetonitrile (ACN and isopropyl alcohol (IPA in an isocratic ratio of 70:30 at a flow rate of 1.0 mL/min with the eluent monitored at 360 nm. The method was validated for specificity, linearity, precision, accuracy and robustness. The calibration plot was linear over the concentration range of 50–150 μg/mL with a correlation coefficient (r2 of 0.999. The proposed method was used to investigate the degradation kinetics of acitretin under the different degradative conditions. The degradation rate constant (K, half-life (t1/2, and t90 were calculated. Degradation of acitretin followed pseudo-first-order kinetics. The drug was found to be less stable under acidic and photolytic degradation conditions: the photolytic degradation constants for acitretin in sunlight and UV light were 0.002698% and 0.0008402% min−1, respectively. The LOD for acitretin and the known impurities were at a level below 0.02%. The method shows consistent recoveries for ACTR (99.8%–101.2% and also for its known impurities (97.2–101.3%. The method was found to be accurate, precise, linear, specific, sensitive, rugged, robust, and useful for characterizing the stability of this chemical.

  16. LLNL Chemical Kinetics Modeling Group

    Energy Technology Data Exchange (ETDEWEB)

    Pitz, W J; Westbrook, C K; Mehl, M; Herbinet, O; Curran, H J; Silke, E J

    2008-09-24

    The LLNL chemical kinetics modeling group has been responsible for much progress in the development of chemical kinetic models for practical fuels. The group began its work in the early 1970s, developing chemical kinetic models for methane, ethane, ethanol and halogenated inhibitors. Most recently, it has been developing chemical kinetic models for large n-alkanes, cycloalkanes, hexenes, and large methyl esters. These component models are needed to represent gasoline, diesel, jet, and oil-sand-derived fuels.

  17. Kinetic energy absorbing pad

    International Nuclear Information System (INIS)

    Bricmont, R.J.; Hamilton, P.A.; Ming Long Ting, R.

    1981-01-01

    Reactors, fuel processing plants etc incorporate pipes and conduits for fluids under high pressure. Fractures, particularly adjacent to conduit elbows, produce a jet of liquid which whips the broken conduit at an extremely high velocity. An enormous impact load would be applied to any stationary object in the conduit's path. The design of cellular, corrugated metal impact pads to absorb the kinetic energy of the high velocity conduits is given. (U.K.)

  18. Calcite Dissolution Kinetics

    Science.gov (United States)

    Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.

    2016-12-01

    A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations 500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics of dissolution. The interplay of mineral

  19. Super-resolution

    DEFF Research Database (Denmark)

    Nasrollahi, Kamal; Moeslund, Thomas B.

    2014-01-01

    Super-resolution, the process of obtaining one or more high-resolution images from one or more low-resolution observations, has been a very attractive research topic over the last two decades. It has found practical applications in many real world problems in different fields, from satellite...

  20. Degradation kinetics of metronidazole and its mutual prodrug with ...

    African Journals Online (AJOL)

    Dr Renu Chadha

    present paper utilizes this technique to monitor the hydrolytic degradation of metronidazole ... the antiprotozoal and anaerobic antibacterial effects of metronidazole with ... The catalytic rate constant for hydrogen ion (kH) and hydroxyl ion (kOH) ...

  1. Spectroscopy and reaction kinetics of HCO

    International Nuclear Information System (INIS)

    Guo, Yili.

    1989-01-01

    The high-resolution infrared spectrum of the C-H stretching fundamental of HCO has been studied by means of infrared flash kinetic spectroscopy. HCO was generated by flash photolysis of acetaldehyde or formaldehyde using a 308 nm (XeCl) excimer laser. The transient absorption was probed with an infrared difference frequency laser system. The high resolution spectra obtained were assigned and fitted with rotational, spin-rotational, and centrifugal distortion constants. The ν 1 band origin is 2434.48 cm/sup /minus/1/. New ground state constants have been derived from a least-squares fit combining the ν 1 data with previous microwave and FIR LMR measurements. A new set of spectroscopic constants for the (1, 0, 0) state, the equilibrium rotational constants, and the orientation of the transition dipole moment are also reported. The kinetics and product branching ratios of the HCO + NO 2 reaction have been studied using visible and infrared laser flash kinetic spectroscopy. The rate constant for the disappearance of HCO radical at 296 K is (5.7 +- 0.9) /times/ 10/sup /minus/11/ cm 3 molec/sup /minus/1/ sec/sup /minus/1/, and it is independent of the pressure of SF 6 buffer gas up to 700 torr. Less than 10% of the reaction goes through the most exothermic product channel, HNO + CO 2 . The product channel, H + CO 2 + NO, is responsible for 52% of the reaction. HONO has been observed, though not quantitatively, as a reaction product corresponding to the HONO + CO channel. 51 refs., 21 figs., 8 tabs

  2. Infrared absorption spectroscopy and chemical kinetics of free radicals

    Energy Technology Data Exchange (ETDEWEB)

    Curl, R.F.; Glass, G.P. [Rice Univ., Houston, TX (United States)

    1993-12-01

    This research is directed at the detection, monitoring, and study of chemical kinetic behavior by infrared absorption spectroscopy of small free radical species thought to be important intermediates in combustion. During the last year, infrared kinetic spectroscopy using excimer laser flash photolysis and color-center laser probing has been employed to study the high resolution spectrum of HCCN, the rate constant of the reaction between ethynyl (C{sub 2}H) radical and H{sub 2} in the temperature region between 295 and 875 K, and the recombination rate of propargyl (CH{sub 2}CCH) at room temperature.

  3. A coupled photometric assay for characterization of S-adenosyl-l-homocysteine hydrolases in the physiological hydrolytic direction.

    Science.gov (United States)

    Kailing, Lyn L; Bertinetti, Daniela; Herberg, Friedrich W; Pavlidis, Ioannis V

    2017-10-25

    S-Adenosyl-l-homocysteine hydrolases (SAHases) are important metabolic enzymes and their dysregulation is associated with some severe diseases. In vivo they catalyze the hydrolysis of S-adenosyl-l-homocysteine (SAH), the by-product of methylation reactions in various organisms. SAH is a potent inhibitor of methyltransferases, thus its removal from the equilibrium is an important requirement for methylation reactions. SAH hydrolysis is also the first step in the cellular regeneration process of the methyl donor S-adenosyl-l-methionine (SAM). However, in vitro the equilibrium lies towards the synthetic direction. To enable characterization of SAHases in the physiologically relevant direction, we have developed a coupled photometric assay that shifts the equilibrium towards hydrolysis by removing the product adenosine, using a high affinity adenosine kinase (AK). This converts adenosine to AMP and thereby forms equimolar amounts of ADP, which is phosphorylated by a pyruvate kinase (PK), in turn releasing pyruvate. The readout of the assay is the consumption of NADH during the lactate dehydrogenase (LDH) catalyzed reduction of pyruvate to lactic acid. The applicability of the assay is showcased for the determination of the kinetic constants of an SAHase from Bradyrhizobium elkanii (K M,SAH 41±5μM, v max,SAH 25±1μM/min with 0.13mg/mL enzyme). This assay is a valuable tool for in vitro characterization of SAHases with biotechnological potential, and for monitoring SAHase activity in diagnostics. Copyright © 2017 Elsevier B.V. All rights reserved.

  4. Kinetics of tetrataenite disordering

    International Nuclear Information System (INIS)

    Dos Santos, E.; Gattacceca, J.; Rochette, P.; Fillion, G.; Scorzelli, R.B.

    2015-01-01

    Tetrataenite is a chemically ordered L1 0 -type Fe 50 Ni 50 alloy detected for the first time in 1977 by 57 Fe Mössbauer spectroscopy studies in iron meteorites. The thermal history of meteorites, in particular short thermal events like those associated to hypervelocity impacts, can be constrained by tracing the presence of tetrataenite or its disordering into taenite. The knowledge of the disordering kinetics of tetrataenite, that is associated with changes in its magnetic properties, is still very fragmentary so that the time–temperature history of these meteorites cannot be constrained in details. Furthermore, knowledge of disordering kinetics is important due to potential technological application of tetrataenite as a rare-earth free strong magnet. Thus, this work provides the first time–temperature data for disordering reaction of tetrataenite. We have shown that disordering is not an instantaneous process but is a kinetic limited reaction. It was shown that disordering may take place at any temperature above the order–disorder transition for L 10 superstructure phase (∼320 °C) when the appropriate time-scale is considered. This result means that the apparent Curie point for tetrataenite is not an absolute property in the sense that any estimate of this parameter should be referred to a given time-scale. - Highlights: • The first time–temperature data for tetrataenite disordering reaction is provided. • Previous works does not give a complete picture of tetrataenite disordering. • Apparent Curie temperature of tetrataenite should be referred to a time-scale. • Tetrataenite can be used as a probe to detect thermal/shock events recorded in meteorites

  5. Quantum kinetic Ising models

    International Nuclear Information System (INIS)

    Augusiak, R; Cucchietti, F M; Lewenstein, M; Haake, F

    2010-01-01

    In this paper, we introduce a quantum generalization of classical kinetic Ising models (KIM), described by a certain class of quantum many-body master equations. Similarly to KIMs with detailed balance that are equivalent to certain Hamiltonian systems, our models reduce to a set of Hamiltonian systems determining the dynamics of the elements of the many-body density matrix. The ground states of these Hamiltonians are well described by the matrix product, or pair entangled projected states. We discuss critical properties of such Hamiltonians, as well as entanglement properties of their low-energy states.

  6. Cysteine residues 244 and 458–459 within the catalytic subunit of Na,K-ATPase control the enzyme's hydrolytic and signaling function under hypoxic conditions

    Directory of Open Access Journals (Sweden)

    Irina Yu. Petrushanko

    2017-10-01

    Full Text Available Our previous findings suggested that reversible thiol modifications of cysteine residues within the actuator (AD and nucleotide binding domain (NBD of the Na,K-ATPase may represent a powerful regulatory mechanism conveying redox- and oxygen-sensitivity of this multifunctional enzyme. S-glutathionylation of Cys244 in the AD and Cys 454-458-459 in the NBD inhibited the enzyme and protected cysteines’ thiol groups from irreversible oxidation under hypoxic conditions. In this study mutagenesis approach was used to assess the role these cysteines play in regulation of the Na,K-ATPase hydrolytic and signaling functions. Several constructs of mouse α1 subunit of the Na,K-ATPase were produced in which Cys244, Cys 454-458-459 or Cys 244-454-458-459 were replaced by alanine. These constructs were expressed in human HEK293 cells. Non-transfected cells and those expressing murine α1 subunit were exposed to hypoxia or treated with oxidized glutathione (GSSG. Both conditions induced inhibition of the wild type Na,K-ATPase. Enzymes containing mutated mouse α1 lacking Cys244 or all four cysteines (Cys 244-454-458-459 were insensitive to hypoxia. Inhibitory effect of GSSG was observed for wild type murine Na,K-ATPase, but was less pronounced in Cys454-458-459Ala mutant and completely absent in the Cys244Ala and Cys 244-454-458-459Ala mutants. In cells, expressing wild type enzyme, ouabain induced activation of Src and Erk kinases under normoxic conditions, whereas under hypoxic conditions this effect was inversed. Cys454-458-459Ala substitution abolished Src kinase activation in response to ouabain treatment, uncoupled Src from Erk signaling, and interfered with O2-sensitivity of Na,K-ATPase signaling function. Moreover, modeling predicted that S-glutathionylation of Cys 458 and 459 should prevent inhibitory binding of Src to NBD. Our data indicate for the first time that cysteine residues within the AD and NBD influence hydrolytic as well as receptor

  7. Kinetics of coal pyrolysis

    Energy Technology Data Exchange (ETDEWEB)

    Seery, D.J.; Freihaut, J.D.; Proscia, W.M. (United Technologies Research Center, East Hartford, CT (USA)); Howard, J.B.; Peters, W.; Hsu, J.; Hajaligol, M.; Sarofim, A. (Massachusetts Inst. of Tech., Cambridge, MA (USA)); Jenkins, R.; Mallin, J.; Espindola-Merin, B. (Pennsylvania State Univ., University Park, PA (USA)); Essenhigh, R.; Misra, M.K. (Ohio State Univ., Columbus, OH (USA))

    1989-07-01

    This report contains results of a coordinated, multi-laboratory investigation of coal devolatilization. Data is reported pertaining to the devolatilization for bituminous coals over three orders of magnitude in apparent heating rate (100 to 100,000 + {degree}C/sec), over two orders of magnitude in particle size (20 to 700 microns), final particle temperatures from 400 to 1600{degree}C, heat transfer modes ranging from convection to radiative, ambient pressure ranging from near vacuum to one atmosphere pressure. The heat transfer characteristics of the reactors are reported in detail. It is assumed the experimental results are to form the basis of a devolatilization data base. Empirical rate expressions are developed for each phase of devolatilization which, when coupled to an awareness of the heat transfer rate potential of a particular devolatilization reactor, indicate the kinetics emphasized by a particular system reactor plus coal sample. The analysis indicates the particular phase of devolatilization that will be emphasized by a particular reactor type and, thereby, the kinetic expressions appropriate to that devolatilization system. Engineering rate expressions are developed from the empirical rate expressions in the context of a fundamental understanding of coal devolatilization developed in the course of the investigation. 164 refs., 223 figs., 44 tabs.

  8. Diffusion Influenced Adsorption Kinetics.

    Science.gov (United States)

    Miura, Toshiaki; Seki, Kazuhiko

    2015-08-27

    When the kinetics of adsorption is influenced by the diffusive flow of solutes, the solute concentration at the surface is influenced by the surface coverage of solutes, which is given by the Langmuir-Hinshelwood adsorption equation. The diffusion equation with the boundary condition given by the Langmuir-Hinshelwood adsorption equation leads to the nonlinear integro-differential equation for the surface coverage. In this paper, we solved the nonlinear integro-differential equation using the Grünwald-Letnikov formula developed to solve fractional kinetics. Guided by the numerical results, analytical expressions for the upper and lower bounds of the exact numerical results were obtained. The upper and lower bounds were close to the exact numerical results in the diffusion- and reaction-controlled limits, respectively. We examined the validity of the two simple analytical expressions obtained in the diffusion-controlled limit. The results were generalized to include the effect of dispersive diffusion. We also investigated the effect of molecular rearrangement of anisotropic molecules on surface coverage.

  9. Chemical kinetics and reaction mechanism

    International Nuclear Information System (INIS)

    Jung, Ou Sik; Park, Youn Yeol

    1996-12-01

    This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

  10. Chemical kinetics of gas reactions

    CERN Document Server

    Kondrat'Ev, V N

    2013-01-01

    Chemical Kinetics of Gas Reactions explores the advances in gas kinetics and thermal, photochemical, electrical discharge, and radiation chemical reactions. This book is composed of 10 chapters, and begins with the presentation of general kinetic rules for simple and complex chemical reactions. The next chapters deal with the experimental methods for evaluating chemical reaction mechanisms and some theories of elementary chemical processes. These topics are followed by discussions on certain class of chemical reactions, including unimolecular, bimolecular, and termolecular reactions. The rema

  11. Adsorption analysis equilibria and kinetics

    CERN Document Server

    Do, Duong D

    1998-01-01

    This book covers topics of equilibria and kinetics of adsorption in porous media. Fundamental equilibria and kinetics are dealt with for homogeneous as well as heterogeneous particles. Five chapters of the book deal with equilibria and eight chapters deal with kinetics. Single component as well as multicomponent systems are discussed. In kinetics analysis, we deal with the various mass transport processes and their interactions inside a porous particle. Conventional approaches as well as the new approach using Maxwell-Stefan equations are presented. Various methods to measure diffusivity, such

  12. ANL high resolution injector

    International Nuclear Information System (INIS)

    Minehara, E.; Kutschera, W.; Hartog, P.D.; Billquist, P.

    1985-01-01

    The ANL (Argonne National Laboratory) high-resolution injector has been installed to obtain higher mass resolution and higher preacceleration, and to utilize effectively the full mass range of ATLAS (Argonne Tandem Linac Accelerator System). Preliminary results of the first beam test are reported briefly. The design and performance, in particular a high-mass-resolution magnet with aberration compensation, are discussed. 7 refs., 5 figs., 2 tabs

  13. The Influence of Solid-State Drawing on Mechanical Properties and Hydrolytic Degradation of Melt-Spun Poly(Lactic Acid (PLA Tapes

    Directory of Open Access Journals (Sweden)

    Fang Mai

    2015-12-01

    Full Text Available The influence of solid-state drawing on the morphology of melt-spun poly(l-lactic acid (PLLA tapes, and the accompanying changes in mechanical and degradation behaviour have been studied. Mechanical properties are found to be strongly dependent on both applied draw ratio and drawing temperature. Moduli of these highly oriented tapes are significantly increased compared to as-extruded tapes at both ambient and elevated temperatures. Interestingly, drawing leads to a significant increase in elongation to break (~3 times and toughness (~13 times compared to as-extruded tapes. Structural and morphological characterization indicates strain-induced crystallization as well as an increase in orientation of the crystalline phase at small strains. Upon further stretching, an “overdrawing” regime is observed, with decreased crystalline orientation due to the breakage of existing crystals. For fixed draw ratios, a significant increase in Young’s modulus and tensile strength is observed with increasing drawing temperature, due to a higher crystallinity and orientation obtained for tapes drawn at higher temperatures. FT-IR results indicate no crystal transformation after drawing, with the α-form being observed in all tapes. Hydrolytic degradability of PLLA was significantly reduced by solid-state drawing.

  14. Characterization of the calcium-fluoroaluminosilicate glass prepared by a non-hydrolytic sol-gel route for future dental application as glass ionomer cement

    Directory of Open Access Journals (Sweden)

    Alexandre Cestari

    2009-06-01

    Full Text Available Glass ionomer cements are widely employed in dentistry due to their physical, biological and mainly anti-caries properties. Glass ionomers consist of an aluminosilicate glass matrix modified with other elements, and they contain large quantities of fluorine. In this study, we report on the preparation of calcium-fluoroaluminosilicate glasses by a nonhydrolytic sol-gel route as an alternative approach to obtaining alumina-silica matrices. The glass powders were prepared via the non-hydrolytic sol-gel method, by mixing AlCl3, SiCl4, CaF2, AlF3, NaF, and AlPO4. The powders were studied by thermal analysis (TG/DTA/DSC, photoluminescence (PL, nuclear magnetic resonance (NMR27Al-29Si, and X ray diffraction (XRD. TG/DTA/DSC analyses revealed a constant mass loss due to structural changes during the heating process, which was confirmed by NMR and PL. A stable aluminosilicate matrix with potential future application as a glass ionomer base was obtained.

  15. Probing the electronic structure of M-graphene oxide (M = Ni, Co, NiCo) catalysts for hydrolytic dehydrogenation of ammonia borane

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Binhua; Liu, Jinyin; Zhou, Litao [Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Material (FUNSOM) and Collaborative Innovation Center of Suzhou Nano Science & Technology, Soochow University, Suzhou 215123 (China); Long, Dan, E-mail: legend_long@aliyun.com [Department of Radiology, Zhejiang Cancer Hospital, Hangzhou 310022 (China); Feng, Kun; Sun, Xuhui [Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Material (FUNSOM) and Collaborative Innovation Center of Suzhou Nano Science & Technology, Soochow University, Suzhou 215123 (China); Zhong, Jun, E-mail: jzhong@suda.edu.cn [Soochow University-Western University Centre for Synchrotron Radiation Research, Institute of Functional Nano and Soft Material (FUNSOM) and Collaborative Innovation Center of Suzhou Nano Science & Technology, Soochow University, Suzhou 215123 (China)

    2016-01-30

    Graphical abstract: An interaction between metal and graphene oxide was probed to enhance the hydrolysis efficiency of ammonia borane. - Highlights: • Various metal elements (M = Ni, Co, NiCo) were dispersed on graphene oxide (GO) for the hydrolysis of ammonia borane (AB). • The electronic structure of the hybrids has been probed by scanning transmission X-ray microscopy (STXM). • An interfacial interaction between metal and GO was observed which could be related to the hydrolysis performance. • The results provide new insight into the enhanced performance of the M-GO hybrids. - Abstract: Various metal elements (M = Ni, Co, NiCo) were dispersed on graphene oxide (GO) to form the M-GO hybrids by a facile way. The hybrids showed good catalytic activities in the hydrolytic dehydrogenation of ammonia borane (AB, NH{sub 3}BH{sub 3}), which were significantly enhanced when compared to the metal nanoparticles or GO alone. The electronic structure of the hybrids has been probed by scanning transmission X-ray microscopy (STXM). The distribution of metal elements was clearly imaged with identical electronic structure. Moreover, an interfacial interaction between metal and GO was observed with the peak intensity proportional to the catalytic performance in the hydrolysis of AB. The results provide new insight into the enhanced performance of the M-GO hybrids and may help for the design of advanced catalysts.

  16. Effects of the toxic dinoflagellate, Gymnodinium catenatum on hydrolytic and antioxidant enzymes, in tissues of the giant lions-paw scallop Nodipecten subnodosus.

    Science.gov (United States)

    Estrada, Norma; de Jesús Romero, Maria; Campa-Córdova, Angel; Luna, Antonio; Ascencio, Felipe

    2007-11-01

    This study documents effects of the toxic dinoflagellate Gymnodinium catenatum, a producer of paralytic shellfish poison, on juvenile farmed (5.9+/-0.39 cm) giant lions-paw scallop Nodipecten subnodosus. Scallops were fed bloom concentrations of toxic dinoflagellate G. catenatum for 7 h. The effect of the toxic dinoflagellate in different tissues was determined by analysis of antioxidant enzymes (catalase, superoxide dismutase, gluthathione peroxidase), thiobarbituric acid reactive substances (lipid peroxidation), and hydrolytic enzymes (proteases, glycosidases, phosphatases, lipases, and esterases). Histopathological photos record the effects of the toxic dinoflagellate in various tissues. The results show that juvenile lions-paw scallops produce pseudo-feces, partially close their shell, increase melanization, and aggregate hemocytes. Several enzymes were affected and could serve as biological markers. In general, the adductor muscle was not affected. In the digestive gland, some enzymes could be the result of defensive and digestive processes. Gills and mantle tissue were markedly affected because these sites respond first to toxic dinoflagellates, leading to the idea that proteolytic cascades could be involved.

  17. Hydrolytic activities of extracellular enzymes in thermophilic and mesophilic anaerobic sequencing-batch reactors treating organic fractions of municipal solid wastes.

    Science.gov (United States)

    Kim, Hyun-Woo; Nam, Joo-Youn; Kang, Seok-Tae; Kim, Dong-Hoon; Jung, Kyung-Won; Shin, Hang-Sik

    2012-04-01

    Extracellular enzymes offer active catalysis for hydrolysis of organic solid wastes in anaerobic digestion. To evidence the quantitative significance of hydrolytic enzyme activities for major waste components, track studies of thermophilic and mesophilic anaerobic sequencing-batch reactors (TASBR and MASBR) were conducted using a co-substrate of real organic wastes. During 1day batch cycle, TASBR showed higher amylase activity for carbohydrate (46%), protease activity for proteins (270%), and lipase activity for lipids (19%) than MASBR. In particular, the track study of protease identified that thermophilic anaerobes degraded protein polymers much more rapidly. Results revealed that differences in enzyme activities eventually affected acidogenic and methanogenic performances. It was demonstrated that the superior nature of enzymatic capability at thermophilic condition led to successive high-rate acidogenesis and 32% higher CH(4) recovery. Consequently, these results evidence that the coupling thermophilic digestion with sequencing-batch operation is a viable option to promote enzymatic hydrolysis of organic particulates. Copyright © 2012 Elsevier Ltd. All rights reserved.

  18. Dead Pericarps of Dry Fruits Function as Long-Term Storage for Active Hydrolytic Enzymes and Other Substances That Affect Germination and Microbial Growth

    Directory of Open Access Journals (Sweden)

    James Godwin

    2017-12-01

    Full Text Available It is commonly assumed that dead pericarps of dry indehiscent fruits have evolved to provide an additional physical layer for embryo protection and as a means for long distance dispersal. The pericarps of dry fruits undergo programmed cell death (PCD during maturation whereby most macromolecules such DNA, RNA, and proteins are thought to be degraded and their constituents remobilized to filial tissues such as embryo and endosperm. We wanted to test the hypothesis that the dead pericarp represents an elaborated layer that is capable of storing active proteins and other substances for increasing survival rate of germinating seeds. Using in gel assays we found that dead pericarps of both dehiscent and indehiscent dry fruits of various plant species including Arabidopsis thaliana and Sinapis alba release upon hydration multiple active hydrolytic enzymes that can persist in an active form for decades, including nucleases, proteases, and chitinases. Proteomic analysis of indehiscent pericarp of S. alba revealed multiple proteins released upon hydration, among them proteases and chitinases, as well as proteins involved in reactive oxygen species (ROS detoxification and cell wall modification. Pericarps appear to function also as a nutritional element-rich storage for nitrate, potassium, phosphorus, sulfur, and others. Sinapis alba dehiscent and indehiscent pericarps possess germination inhibitory substances as well as substances that promote microbial growth. Collectively, our study explored previously unknown features of the dead pericarp acting also as a reservoir of biological active proteins, and other substances capable of “engineering” the microenvironment for the benefit of the embryo.

  19. Influence of organic load rate (OLR) on the hydrolytic acidification of 2-butenal manufacture wastewater and analysis of bacterial community structure.

    Science.gov (United States)

    Song, Guangqing; Xi, Hongbo; Zhou, Yuexi; Fu, Liya; Xing, Xin; Wu, Changyong

    2017-11-01

    The influence of organic loading rate (OLR) on the performance of hydrolytic acidification process for treating 2-butenal manufacture wastewater was comprehensively studied, while its impact on microbial community was thoroughly investigated. The results demonstrated that over 21.0% of the average COD removal rate was observed in the range of OLR from 0.52 to 3.98g COD/L·d, whereas it reduced to 15.3% with increasing OLR to 6.09g COD/L·d. The acidification degree dramatically decreased from 17.1% to 4.7% when OLR increased from 3.98 to 6.09g COD/L·d. In addition, the removal rates of three kinds of typical matters were less than 65% at the OLR 6.09g COD/L·d. Illumina MiSeq sequencing revealed that Proteobacteria, Chloroflexi, Firmicutes, and Bacteroidetes were dominant phyla at different OLRs. Finally, multivariate analysis suggested that the genera Longilinea and T78 had a positive correlation with the degradation of three kinds of typical matters and COD removal rates. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Study of kinetics of 2,3-diphosphoglycerate degradation by 31P-NMR technique in depleted human erythrocytes

    International Nuclear Information System (INIS)

    Ataullakhanov, F.I.; Vitvitskii, V.M.; Dubinskaya, E.I.; Dubinskii, V.Z.

    1986-01-01

    The kinetics of 2,3-diphosphoglycerate degradation in depleted human erythrocytes was studied by the high-resolution 31 P-NMR technique. A plateau was found on the kinetic curve in the first 1.5-2 h after the beginning of depletion. The mechanisms that may be responsible for the existence of such a plateau are discussed

  1. Kinetics of Social Contagion

    Science.gov (United States)

    Ruan, Zhongyuan; Iñiguez, Gerardo; Karsai, Márton; Kertész, János

    2015-11-01

    Diffusion of information, behavioral patterns or innovations follows diverse pathways depending on a number of conditions, including the structure of the underlying social network, the sensitivity to peer pressure and the influence of media. Here we study analytically and by simulations a general model that incorporates threshold mechanism capturing sensitivity to peer pressure, the effect of "immune" nodes who never adopt, and a perpetual flow of external information. While any constant, nonzero rate of dynamically introduced spontaneous adopters leads to global spreading, the kinetics by which the asymptotic state is approached shows rich behavior. In particular, we find that, as a function of the immune node density, there is a transition from fast to slow spreading governed by entirely different mechanisms. This transition happens below the percolation threshold of network fragmentation, and has its origin in the competition between cascading behavior induced by adopters and blocking due to immune nodes. This change is accompanied by a percolation transition of the induced clusters.

  2. The temperature hydration kinetics

    Directory of Open Access Journals (Sweden)

    Mircea Oroian

    2017-07-01

    Full Text Available The aim of this study is to evaluate the hydration kinetics of lentil seeds (Lens culinaris in water at different temperatures (25, 32.5, 40, 55, 70 and 80 °C for assessing the adequacy of models for describing the absorption phenomena during soaking. The diffusion coefficient values were calculated using Fick’s model for spherical and hemispherical geometries and the values were in the range of 10−6 m2/s. The experimental data were fitted to Peleg, Sigmoidal, Weibull and Exponential models. The models adequacy was determined using regression coefficients (R2, root mean square error (RMSE and reduced chi-square (χ2. The Peleg model is the suitable one for predicting the experimental data. Temperature had a positive and significant effect on the water absorption capacities and absorption was an endothermic process.

  3. Kinetic theory of Jeans instability

    NARCIS (Netherlands)

    Trigger, S.A.; Ershkovic, A.I.; Heijst, van G.J.F.; Schram, P.P.J.M.

    2004-01-01

    Kinetic treatment of the Jeans gravitational instability, with collisions taken into account, is presented. The initial-value problem for the distribution function which obeys the kinetic equation, with the collision integral conserving the number of particles, is solved. Dispersion relation is

  4. Automated conflict resolution issues

    Science.gov (United States)

    Wike, Jeffrey S.

    1991-01-01

    A discussion is presented of how conflicts for Space Network resources should be resolved in the ATDRSS era. The following topics are presented: a description of how resource conflicts are currently resolved; a description of issues associated with automated conflict resolution; present conflict resolution strategies; and topics for further discussion.

  5. Role of tomography in providing radionuclide distribution and kinetic data

    International Nuclear Information System (INIS)

    Budinger, T.F.; Derenzo, S.E.; Huesman, R.H.

    1981-01-01

    A major limitation in radionuclide dosimetry has been the lack of human organ-specific radionuclide distribution and kinetic data because methods of acquiring sequential quantitative information from volumes of interest were not available. Developments in emission computed tomography instrumentation and associated algorithms have overcome this basic limitation, thus allowing in vivo noninvasive tissue distribution studies to be performed. Five aspects of kinetic data acquisition using tomography are: (1) the resolution volume for quantitative work is about two times larger than the system resolution element size as defined by a spread function criterion of full width at half (peak) maximum; (2) scattered radiation might account for 30% of the activity in a given resolution volume and must be taken into account for accurate calculations; (3) proper attenuation compensation must be made to yield quantitative data, particularly with single photon tomography; (4) for dosimetry studies with short half-life labels, multisection systems with dynamic imaging capabilities commensurate with the half-life are needed; (5) the biological conditions such as patient disease and dietary history and the specific activity of the radiopharmaceutical are factors of prime importance in the distribution kinetics

  6. Spectroscopy, Kinetics, and Dynamics of Combustion Radicals

    Energy Technology Data Exchange (ETDEWEB)

    Nesbitt, David J. [Research/Professor

    2013-08-06

    Spectroscopy, kinetics and dynamics of jet cooled hydrocarbon transients relevant to the DOE combustion mission have been explored, exploiting i) high resolution IR lasers, ii) slit discharge sources for formation of jet cooled radicals, and iii) high sensitivity detection with direct laser absorption methods and near the quantum shot noise limit. What makes this combination powerful is that such transients can be made under high concentrations and pressures characteristic of actual combustion conditions, and yet with the resulting species rapidly cooled (T ≈10-15K) in the slit supersonic expansion. Combined with the power of IR laser absorption methods, this provides novel access to spectral detection and study of many critical combustion species.

  7. Optimal Bayesian Experimental Design for Combustion Kinetics

    KAUST Repository

    Huan, Xun

    2011-01-04

    Experimental diagnostics play an essential role in the development and refinement of chemical kinetic models, whether for the combustion of common complex hydrocarbons or of emerging alternative fuels. Questions of experimental design—e.g., which variables or species to interrogate, at what resolution and under what conditions—are extremely important in this context, particularly when experimental resources are limited. This paper attempts to answer such questions in a rigorous and systematic way. We propose a Bayesian framework for optimal experimental design with nonlinear simulation-based models. While the framework is broadly applicable, we use it to infer rate parameters in a combustion system with detailed kinetics. The framework introduces a utility function that reflects the expected information gain from a particular experiment. Straightforward evaluation (and maximization) of this utility function requires Monte Carlo sampling, which is infeasible with computationally intensive models. Instead, we construct a polynomial surrogate for the dependence of experimental observables on model parameters and design conditions, with the help of dimension-adaptive sparse quadrature. Results demonstrate the efficiency and accuracy of the surrogate, as well as the considerable effectiveness of the experimental design framework in choosing informative experimental conditions.

  8. Kinetics of thyroid hormones

    International Nuclear Information System (INIS)

    Inada, Mitsuo; Nishikawa, Mitsushige; Naito, Kimikazu; Ishii, Hitoshi; Tanaka, Kiyoshi

    1980-01-01

    Kinetics of thyroid hormones were outlined, and recent progress in metabolism of these hormones was also described. Recently, not only T 4 and T 3 but also rT 3 , 3,3'-T 2 , 3',5'-T 2 , and 3,5-T 2 can be measured by RIA. To clarify metabolic pathways of these hormones, metabolic clearance rate and production rate of these hormones were calculated. As single-compartment analysis was insufficient to clarify disappearance curves of thyroid hormones in blood such as T 3 and T 2 of which metabolic speed was so fast, multi-compartment analysis or non-compartment analysis were also performed. Thyroid hormones seemed to be measured more precisely by constant infusion method. At the first step of T 4 metabolism, T 3 was formed by 5'-monodeiodination of T 4 , and rT 3 was formed by 5-monodeiodination of T 4 . As metabolic pathways of T 3 and rT 3 , conversion of them to 3,3'-T 2 or to 3',5'-T 2 and 3,5-T 2 was supposed. This subject will be an interesting research theme in future. (Tsunoda, M.)

  9. Bank Resolution in Europe

    DEFF Research Database (Denmark)

    N. Gordon, Jeffery; Ringe, Georg

    2015-01-01

    Bank resolution is a key pillar of the European Banking Union. This column argues that the current structure of large EU banks is not conducive to an effective and unbiased resolution procedure. The authors would require systemically important banks to reorganise into a ‘holding company’ structure......, where the parent company holds unsecured term debt sufficient to cover losses at its operating financial subsidiaries. This would facilitate a ‘single point of entry’ resolution procedure, minimising the risk of creditor runs and destructive ring-fencing by national regulators....

  10. Effect of Different Lignocellulosic Diets on Bacterial Microbiota and Hydrolytic Enzyme Activities in the Gut of the Cotton Boll Weevil (Anthonomus grandis).

    Science.gov (United States)

    Ben Guerrero, Emiliano; Soria, Marcelo; Salvador, Ricardo; Ceja-Navarro, Javier A; Campos, Eleonora; Brodie, Eoin L; Talia, Paola

    2016-01-01

    Cotton boll weevils, Anthonomus grandis , are omnivorous coleopteran that can feed on diets with different compositions, including recalcitrant lignocellulosic materials. We characterized the changes in the prokaryotic community structure and the hydrolytic activities of A. grandis larvae fed on different lignocellulosic diets. A. grandis larvae were fed on three different artificial diets: cottonseed meal (CM), Napier grass (NG) and corn stover (CS). Total DNA was extracted from the gut samples for amplification and sequencing of the V3-V4 hypervariable region of the 16S rRNA gene. Proteobacteria and Firmicutes dominated the gut microbiota followed by Actinobacteria, Spirochaetes and a small number of unclassified phyla in CM and NG microbiomes. In the CS feeding group, members of Spirochaetes were the most prevalent, followed by Proteobacteria and Firmicutes. Bray-Curtis distances showed that the samples from the CS community were clearly separated from those samples of the CM and NG diets. Gut extracts from all three diets exhibited endoglucanase, xylanase, β-glucosidase and pectinase activities. These activities were significantly affected by pH and temperature across different diets. We observed that the larvae reared on a CM showed significantly higher activities than larvae reared on NG and CS. We demonstrated that the intestinal bacterial community structure varies depending on diet composition. Diets with more variable and complex compositions, such as CS, showed higher bacterial diversity and richness than the two other diets. In spite of the detected changes in composition and diversity, we identified a core microbiome shared between the three different lignocellulosic diets. These results suggest that feeding with diets of different lignocellulosic composition could be a viable strategy to discover variants of hemicellulose and cellulose breakdown systems.

  11. Preparation and characterization of LTA-type zeolite framework dispersed ruthenium nanoparticles and their catalytic application in the hydrolytic dehydrogenation of ammonia–borane for efficient hydrogen generation

    International Nuclear Information System (INIS)

    Zahmakiran, Mehmet

    2012-01-01

    Highlights: ► Ru(0)NPs-ZK-4 were prepared and characterized by advanced analytical techniques. ► They achieve the hydrolysis of ammonia-borane with TOF = 5410 h −1 and TTO = 36700. ► They maintain 85% of their activity even at the fifth catalytic run. - Abstract: The safe and efficient hydrogen storage and production are major obstacles to use hydrogen as an energy carrier. Therefore, significant efforts have been focused on the development of new materials for the chemical hydrogen storage and production. Of particular importance, ammonia–borane (NH 3 BH 3 ) is emerging as one of the most promising solid hydrogen carrier due to its high gravimetric hydrogen storage capacity (19.6 wt.%) and low molecular weight (30.8 g/mol). ammonia–borane can release hydrogen gas upon catalytic hydrolysis under mild conditions. Herein, the discovery of a new catalytic material, ruthenium nanoparticles stabilized by ZK-4 zeolite framework, for this important reaction has been reported. This new catalyst system was prepared by borohydride reduction of ruthenium(III)-exchanged ZK-4 zeolite in water at room temperature. The characterization of the resulting material by advanced analytical tools shows the formation of ZK-4 zeolite dispersed ruthenium nanoparticles (2.9 ± 0.9 nm). The catalytic performance of the resulting supported ruthenium nanoparticles depending on activity, lifetime and reusability was demonstrated in the hydrolytic dehydrogenation of ammonia–borane. They were found to be highly active (initial TOF = 5410 h −1 ), long-lived (TTO = 36,700) and reusable catalyst (retaining of >85% of initial activity in the 5th reuse) in this important catalytic reaction at room temperature under air.

  12. Kinetic effects on magnetohydrodynamic phenomena

    International Nuclear Information System (INIS)

    Naito, Hiroshi; Matsumoto, Taro

    2001-01-01

    Resistive and ideal magnetohydrodynamic (MHD) theories are insufficient to adequately explain MHD phenomena in the high-temperature plasma. Recent progress in numerical simulations concerning kinetic effects on magnetohydrodynamic phenomena is summarized. The following three topics are studied using various models treating extended-MHD phenomena. (1) Kinetic modifications of internal kink modes in tokamaks with normal and reversed magnetic shear configurations. (2) Temporal evolution of the toroidal Alfven eigenmode and fishbone mode in tokamaks with energetic ions. (3) Kinetic stabilization of a title mode in field-reversed configurations by means of anchoring ions and beam ions. (author)

  13. Detection of kinetic change points in piece-wise linear single molecule motion

    Science.gov (United States)

    Hill, Flynn R.; van Oijen, Antoine M.; Duderstadt, Karl E.

    2018-03-01

    Single-molecule approaches present a powerful way to obtain detailed kinetic information at the molecular level. However, the identification of small rate changes is often hindered by the considerable noise present in such single-molecule kinetic data. We present a general method to detect such kinetic change points in trajectories of motion of processive single molecules having Gaussian noise, with a minimum number of parameters and without the need of an assumed kinetic model beyond piece-wise linearity of motion. Kinetic change points are detected using a likelihood ratio test in which the probability of no change is compared to the probability of a change occurring, given the experimental noise. A predetermined confidence interval minimizes the occurrence of false detections. Applying the method recursively to all sub-regions of a single molecule trajectory ensures that all kinetic change points are located. The algorithm presented allows rigorous and quantitative determination of kinetic change points in noisy single molecule observations without the need for filtering or binning, which reduce temporal resolution and obscure dynamics. The statistical framework for the approach and implementation details are discussed. The detection power of the algorithm is assessed using simulations with both single kinetic changes and multiple kinetic changes that typically arise in observations of single-molecule DNA-replication reactions. Implementations of the algorithm are provided in ImageJ plugin format written in Java and in the Julia language for numeric computing, with accompanying Jupyter Notebooks to allow reproduction of the analysis presented here.

  14. High Resolution Elevation Contours

    Data.gov (United States)

    Minnesota Department of Natural Resources — This dataset contains contours generated from high resolution data sources such as LiDAR. Generally speaking this data is 2 foot or less contour interval.

  15. Ultra high resolution tomography

    Energy Technology Data Exchange (ETDEWEB)

    Haddad, W.S.

    1994-11-15

    Recent work and results on ultra high resolution three dimensional imaging with soft x-rays will be presented. This work is aimed at determining microscopic three dimensional structure of biological and material specimens. Three dimensional reconstructed images of a microscopic test object will be presented; the reconstruction has a resolution on the order of 1000 A in all three dimensions. Preliminary work with biological samples will also be shown, and the experimental and numerical methods used will be discussed.

  16. High resolution positron tomography

    International Nuclear Information System (INIS)

    Brownell, G.L.; Burnham, C.A.

    1982-01-01

    The limits of spatial resolution in practical positron tomography are examined. The four factors that limit spatial resolution are: positron range; small angle deviation; detector dimensions and properties; statistics. Of these factors, positron range may be considered the fundamental physical limitation since it is independent of instrument properties. The other factors are to a greater or lesser extent dependent on the design of the tomograph

  17. Scalable Resolution Display Walls

    KAUST Repository

    Leigh, Jason; Johnson, Andrew; Renambot, Luc; Peterka, Tom; Jeong, Byungil; Sandin, Daniel J.; Talandis, Jonas; Jagodic, Ratko; Nam, Sungwon; Hur, Hyejung; Sun, Yiwen

    2013-01-01

    This article will describe the progress since 2000 on research and development in 2-D and 3-D scalable resolution display walls that are built from tiling individual lower resolution flat panel displays. The article will describe approaches and trends in display hardware construction, middleware architecture, and user-interaction design. The article will also highlight examples of use cases and the benefits the technology has brought to their respective disciplines. © 1963-2012 IEEE.

  18. Resolution 1540 (2004) overview

    International Nuclear Information System (INIS)

    Kasprzyk, N.

    2013-01-01

    This series of slides presents the Resolution 1540, its features and its status of implementation. Resolution 1540 is a response to the risk that non-State actors may acquire, develop, traffic in weapons of mass destruction and their means of delivery. Resolution 1540 was adopted on 28 April 2004 by the U.N. Security Council at the unanimity of its members. Resolution 1540 deals with the 3 kinds of weapons of mass destruction (nuclear, chemical and biological weapons) as well as 'related materials'. This resolution implies 3 sets of obligations: first no support of non-state actors concerning weapons of mass destruction, secondly to set national laws that prohibit any non-state actors to deal with weapons of mass destruction and thirdly to enforce domestic control to prevent the proliferation of nuclear, chemical or biological weapons and their means of delivery. Four working groups operated by the 1540 Committee have been settled: - Implementation (coordinator: Germany); - Assistance (coordinator: France); - International cooperation (interim coordinator: South Africa); and - Transparency and media outreach (coordinator: USA). The status of implementation of the resolution continues to improve since 2004, much work remains to be done and the gravity of the threat remains considerable. (A.C.)

  19. Microbial respiration and kinetics of extracellular enzymes activities through rhizosphere and detritusphere at agricultural site

    Science.gov (United States)

    Löppmann, Sebastian; Blagodatskaya, Evgenia; Kuzyakov, Yakov

    2014-05-01

    Rhizosphere and detritusphere are soil microsites with very high resource availability for microorganisms affecting their biomass, composition and functions. In the rhizosphere low molecular compounds occur with root exudates and low available polymeric compounds, as belowground plant senescence. In detritusphere the substrate for decomposition is mainly a polymeric material of low availability. We hypothesized that microorganisms adapted to contrasting quality and availability of substrates in the rhizosphere and detritusphere are strongly different in affinity of hydrolytic enzymes responsible for decomposition of organic compounds. According to common ecological principles easily available substrates are quickly consumed by microorganisms with enzymes of low substrate affinity (i.e. r-strategists). The slow-growing K-strategists with enzymes of high substrate affinity are better adapted for growth on substrates of low availability. Estimation of affinity of enzyme systems to the substrate is based on Michaelis-Menten kinetics, reflecting the dependency of decomposition rates on substrate amount. As enzymes-mediated reactions are substrate-dependent, we further hypothesized that the largest differences in hydrolytic activity between the rhizosphere and detritusphere occur at substrate saturation and that these differences are smoothed with increasing limitation of substrate. Affected by substrate limitation, microbial species follow a certain adaptation strategy. To achieve different depth gradients of substrate availability 12 plots on an agricultural field were established in the north-west of Göttingen, Germany: 1) 4 plots planted with maize, reflecting lower substrate availability with depth; 2) 4 unplanted plots with maize litter input (0.8 kg m-2 dry maize residues), corresponding to detritusphere; 3) 4 bare fallow plots as control. Maize litter was grubbed homogenously into the soil at the first 5 cm to ensure comparable conditions for the herbivore and

  20. Bicarbonate kinetics in Indian males

    Indian Academy of Sciences (India)

    Madhu

    ized kinetics of bicarbonate using a three-compartment model, to assess which compartmental fluxes changed dur- .... total VCO2 was < 3 % and the average respiratory quotient ..... a part of the nonrespiratory losses of 13CO2 occur to this.

  1. Kinetic equations in dirty superconductors

    International Nuclear Information System (INIS)

    Kraehenbuehl, Y.

    1981-01-01

    Kinetic equations for superconductors in the dirty limit are derived using a method developed for superfluid systems, which allows a systematic expansion in small parameters; exact charge conservation is obeyed. (orig.)

  2. Cell kinetics and therapeutic efficiency

    International Nuclear Information System (INIS)

    Andreeff, M.; Abenhardt, W.; Gruner, B.; Stoffner, D.; Mainz Univ.

    1976-01-01

    The study shows that cell kinetics effects correlate with the effects of cytostatic drugs in the tumour model investigated here. It should, however, be noted that even genetically related tumour cell types may react differently to the same cytostatic drug, and that the cell kinetics effects, due to the changes in the cell cycle, cannot be predicted but should be followed with a very fast method, e.g. sequential flan fluorescence cytophotometry, for optimal therapeutic results. (orig./GSE) [de

  3. Kinetic parameters from thermogravimetric analysis

    Science.gov (United States)

    Kiefer, Richard L.

    1993-01-01

    High performance polymeric materials are finding increased use in aerospace applications. Proposed high speed aircraft will require materials to withstand high temperatures in an oxidative atmosphere for long periods of time. It is essential that accurate estimates be made of the performance of these materials at the given conditions of temperature and time. Temperatures of 350 F (177 C) and times of 60,000 to 100,000 hours are anticipated. In order to survey a large number of high performance polymeric materials on a reasonable time scale, some form of accelerated testing must be performed. A knowledge of the rate of a process can be used to predict the lifetime of that process. Thermogravimetric analysis (TGA) has frequently been used to determine kinetic information for degradation reactions in polymeric materials. Flynn and Wall studied a number of methods for using TGA experiments to determine kinetic information in polymer reactions. Kinetic parameters, such as the apparent activation energy and the frequency factor, can be determined in such experiments. Recently, researchers at the McDonnell Douglas Research Laboratory suggested that a graph of the logarithm of the frequency factor against the apparent activation energy can be used to predict long-term thermo-oxidative stability for polymeric materials. Such a graph has been called a kinetic map. In this study, thermogravimetric analyses were performed in air to study the thermo-oxidative degradation of several high performance polymers and to plot their kinetic parameters on a kinetic map.

  4. Gyrocenter-gauge kinetic theory

    International Nuclear Information System (INIS)

    Qin, H.; Tang, W.M.; Lee, W.W.

    2000-01-01

    Gyrocenter-gauge kinetic theory is developed as an extension of the existing gyrokinetic theories. In essence, the formalism introduced here is a kinetic description of magnetized plasmas in the gyrocenter coordinates which is fully equivalent to the Vlasov-Maxwell system in the particle coordinates. In particular, provided the gyroradius is smaller than the scale-length of the magnetic field, it can treat high frequency range as well as the usual low frequency range normally associated with gyrokinetic approaches. A significant advantage of this formalism is that it enables the direct particle-in-cell simulations of compressional Alfven waves for MHD applications and of RF waves relevant to plasma heating in space and laboratory plasmas. The gyrocenter-gauge kinetic susceptibility for arbitrary wavelength and arbitrary frequency electromagnetic perturbations in a homogeneous magnetized plasma is shown to recover exactly the classical result obtained by integrating the Vlasov-Maxwell system in the particle coordinates. This demonstrates that all the waves supported by the Vlasov-Maxwell system can be studied using the gyrocenter-gauge kinetic model in the gyrocenter coordinates. This theoretical approach is so named to distinguish it from the existing gyrokinetic theory, which has been successfully developed and applied to many important low-frequency and long parallel wavelength problems, where the conventional meaning of gyrokinetic has been standardized. Besides the usual gyrokinetic distribution function, the gyrocenter-gauge kinetic theory emphasizes as well the gyrocenter-gauge distribution function, which sometimes contains all the physics of the problems being studied, and whose importance has not been realized previously. The gyrocenter-gauge distribution function enters Maxwell's equations through the pull-back transformation of the gyrocenter transformation, which depends on the perturbed fields. The efficacy of the gyrocenter-gauge kinetic approach is

  5. Crystallization Kinetics within a Generic Modelling Framework

    DEFF Research Database (Denmark)

    Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist

    2013-01-01

    An existing generic modelling framework has been expanded with tools for kinetic model analysis. The analysis of kinetics is carried out within the framework where kinetic constitutive models are collected, analysed and utilized for the simulation of crystallization operations. A modelling...... procedure is proposed to gain the information of crystallization operation kinetic model analysis and utilize this for faster evaluation of crystallization operations....

  6. Study of extraction kinetics of lanthanides(III) and actinides(III) nitrates by the molecule N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide; Etude des cinetiques d'extraction des nitrates de lanthanides (III) et d'actinides (III) par le malonamide N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide

    Energy Technology Data Exchange (ETDEWEB)

    Daldon, M

    1999-07-01

    The kinetics of extraction of lanthanides (III) and actinides (III) nitrates by the molecule N, N'-dimethyl - N, N'-dibutyl tetra-decyl malonamide has been investigated. This study was realised with a new constant interfacial-area-stirred cell. During the qualification step of the device it appears that the reduction of the device can lead to hydrolytic perturbations. The main conclusions are: - after the determination of conditions which provide kinetics regime (diffusion of species neglectable), partial orders of the kinetics law have been obtained and lead to the establishment of the law J = k [Nd{sup 3+}] [NO{sub 3}{sup -}]{sup 3} [diamide]{sup 1}, - interfacial tension measurements and kinetics study in presence of surface-active compounds proved that the chemical limiting reaction for Nd(III) is interfacial, - the results allow to propose an adsorption-desorption reaction mechanism, - a comprehensive study of the extraction kinetics of the lanthanides(III) series and also Am(III) and Cm(III) nitrates has been realised. The lighter lanthanides (La, Ce and Pr) exhibit higher kinetics rate of extraction than the others, which differs from the tendency observed with distribution coefficients which exhibit tetrad effect. The kinetics rate of extraction of Am(III) and Cm(III) is closed to the value of Eu(III). (author)

  7. Evaluation of deltamethrin kinetics and dosimetry in the maturing rat using a PBPK model

    International Nuclear Information System (INIS)

    Tornero-Velez, Rogelio; Mirfazaelian, Ahmad; Kim, Kyu-Bong; Anand, Sathanandam S.; Kim, Hyo J.; Haines, Wendy T.; Bruckner, James V.; Fisher, Jeffrey W.

    2010-01-01

    Immature rats are more susceptible than adults to the acute neurotoxicity of pyrethroid insecticides like deltamethrin (DLM). A companion kinetics study (Kim et al., in press) revealed that blood and brain levels of the neuroactive parent compound were inversely related to age in rats 10, 21, 40 and 90 days old. The objective of the current study was to modify a physiologically based pharmacokinetic (PBPK) model of DLM disposition in the adult male Sprague-Dawley rat (Mirfazaelian et al., 2006), so blood and target organ dosimetry could be accurately predicted during maturation. Age-specific organ weights and age-dependent changes in the oxidative and hydrolytic clearance of DLM were modeled with a generalized Michaelis-Menten model for growth and the summary equations incorporated into the PBPK model. The model's simulations compared favorably with empirical DLM time-courses in plasma, blood, brain and fat for the four age-groups evaluated (10, 21, 40 and 90 days old). PND 10 pups' area under the 24-h brain concentration time curve (AUC 0-24h ) was 3.8-fold higher than that of the PND 90 adults. Our maturing rat PBPK model allows for updating with age- and chemical-dependent parameters, so pyrethroid dosimetry can be forecast in young and aged individuals. Hence, this model provides a methodology for risk assessors to consider age-specific adjustments to oral Reference Doses on the basis of PK differences.

  8. High resolution solar observations

    International Nuclear Information System (INIS)

    Title, A.

    1985-01-01

    Currently there is a world-wide effort to develop optical technology required for large diffraction limited telescopes that must operate with high optical fluxes. These developments can be used to significantly improve high resolution solar telescopes both on the ground and in space. When looking at the problem of high resolution observations it is essential to keep in mind that a diffraction limited telescope is an interferometer. Even a 30 cm aperture telescope, which is small for high resolution observations, is a big interferometer. Meter class and above diffraction limited telescopes can be expected to be very unforgiving of inattention to details. Unfortunately, even when an earth based telescope has perfect optics there are still problems with the quality of its optical path. The optical path includes not only the interior of the telescope, but also the immediate interface between the telescope and the atmosphere, and finally the atmosphere itself

  9. Resolution and termination

    Directory of Open Access Journals (Sweden)

    Adina FOLTIŞ

    2012-01-01

    Full Text Available The resolution, the termination and the reduction of labour conscription are regulated by articles 1549-1554 in the new Civil Code, which represents the common law in this matter. We appreciate that the new regulation does not conclusively clarify the issue related to whether the existence of liability in order to call upon the resolution is necessary or not, because the existence of this condition has been inferred under the previous regulation from the fact that the absence of liability shifts the inexecution issue on the domain of fortuitous impossibility of execution, situation in which the resolution of the contract is not in question, but that of the risk it implies.

  10. Spatial Inhomogeneity of Kinetic and Magnetic Dissipations in Thermal Convection

    Energy Technology Data Exchange (ETDEWEB)

    Hotta, H. [Department of Physics, Graduate School of Science, Chiba university, 1-33 Yayoi-cho, Inage-ku, Chiba, 263-8522 (Japan)

    2017-08-20

    We investigate the inhomogeneity of kinetic and magnetic dissipations in thermal convection using high-resolution calculations. In statistically steady turbulence, the injected and dissipated energies are balanced. This means that a large amount of energy is continuously converted into internal energy via dissipation. As in thermal convection, downflows are colder than upflows and the inhomogeneity of the dissipation potentially changes the convection structure. Our investigation of the inhomogeneity of the dissipation shows the following. (1) More dissipation is seen around the bottom of the calculation domain, and this tendency is promoted with the magnetic field. (2) The dissipation in the downflow is much larger than that in the upflow. The dissipation in the downflow is more than 80% of the total at maximum. This tendency is also promoted with the magnetic field. (3) Although 2D probability density functions of the kinetic and magnetic dissipations versus the vertical velocity are similar, the kinetic and magnetic dissipations are not well correlated. Our result suggests that the spatial inhomogeneity of the dissipation is significant and should be considered when modeling a small-scale strong magnetic field generated with an efficient small-scale dynamo for low-resolution calculations.

  11. High resolution drift chambers

    International Nuclear Information System (INIS)

    Va'vra, J.

    1985-07-01

    High precision drift chambers capable of achieving less than or equal to 50 μm resolutions are discussed. In particular, we compare so called cool and hot gases, various charge collection geometries, several timing techniques and we also discuss some systematic problems. We also present what we would consider an ''ultimate'' design of the vertex chamber. 50 refs., 36 figs., 6 tabs

  12. Transformation kinetics for nucleus clusters

    International Nuclear Information System (INIS)

    Villa, Elena; Rios, Paulo R.

    2009-01-01

    A rigorous mathematical approach based on stochastic geometry concepts is presented to extend previous Johnson-Mehl, Avrami, Kolmogorov treatment of transformation kinetics to situations in which nuclei are not homogeneously located in space but are located in clusters. An exact analytical solution is presented here for the first time assuming that nucleation sites follow a Matern cluster process. The influence of Matern cluster process parameters on subsequent growth kinetics and the microstructural path are illustrated by means of numerical examples. Moreover, using the superposition principle, exact analytical solutions are also obtained when nucleation takes place by a combination of a Matern cluster process and an inhomogeneous Poisson point process. The new solutions presented here significantly increase the number of exactly solvable cases available to formal kinetics.

  13. Chapter 22. Cell population kinetics

    International Nuclear Information System (INIS)

    Tubiana, M.

    1975-01-01

    The main contribution of radioisotopes to the development of a new discipline, cell population kinetics, was shown. The aim of this science is to establish, for each tissue of the organism, the life span of its component cells and the mechanisms governing its growth, its differentiation and its homeostasis with respect to outside attacks. Labelling techniques have been used to follow the cells during these various processes. The case of non-dividing cells was considered first, taking as example, the red blood cells of which the lifetime was studied, after which the case of proliferating cells was examined using 14 C- or tritium-labelled thymidine. The methods used to measure the cell cycle parameters were described: labelled-mitosis curve method, double-labelling and continuous labelling methods, proliferation coefficient measurement. Cell kinetics were shown to allow an interpretation of radiobiological data. Finally the practical value of cell kinetics research was shown [fr

  14. Kinetic theory and transport phenomena

    CERN Document Server

    Soto, Rodrigo

    2016-01-01

    This textbook presents kinetic theory, which is a systematic approach to describing nonequilibrium systems. The text is balanced between the fundamental concepts of kinetic theory (irreversibility, transport processes, separation of time scales, conservations, coarse graining, distribution functions, etc.) and the results and predictions of the theory, where the relevant properties of different systems are computed. The book is organised in thematic chapters where different paradigmatic systems are studied. The specific features of these systems are described, building and analysing the appropriate kinetic equations. Specifically, the book considers the classical transport of charges, the dynamics of classical gases, Brownian motion, plasmas, and self-gravitating systems, quantum gases, the electronic transport in solids and, finally, semiconductors. Besides these systems that are studied in detail, concepts are applied to some modern examples including the quark–gluon plasma, the motion of bacterial suspen...

  15. Morphology and annealing kinetics of ion tracks in minerals

    Directory of Open Access Journals (Sweden)

    Ewing R. C.

    2012-10-01

    Full Text Available We have studied the morphology and annealing kinetics of ion tracks in Durango apatite using synchrotron small angle X-ray scattering. The non-destructive, artefact-free technique enables us to determine the track radii with a resolution of fractions of a nanometre. The tracks were generated using different heavy ions with energies between 185 MeV and 2.6 GeV. The track morphology is consistent with the formation of long cylindrical amorphous tracks. The annealing kinetics, measured by SAXS in combination with ex situ and in situ annealing experiments, suggests structural relaxation followed by recrystallisation of the damaged material. The measurement methodology shown here provides a new means for in-depth studies of ion-track formation in minerals under a wide variety of geological conditions.

  16. Study on the agglomeration kinetics of uranium peroxide

    Energy Technology Data Exchange (ETDEWEB)

    Bertrand, M.; Mojica Rodriguez, L.A. [CEA, Centre de Marcoule, Nuclear Energy Division, RadioChemistry and Process Department, 17171, Bagnols-sur-Ceze 30207 (France); Muhr, H.; Plasari, E. [Reaction and Process Engineering Laboratory, CNRS, University of Lorraine. 1 rue Grandville, BP 20451, Nancy 54001 (France); Auger, F. [Areva Mines/SEPA. 2 route de Lavaugrasse, Bessines-sur-Gartempe 87250 (France)

    2016-07-01

    Considering the previous study dealing with thermodynamic and kinetic phenomena (nucleation and crystal growth) during the uranium peroxide precipitation, this work focuses on the agglomeration mechanism. It provides the results obtained from the experiments carried out in a mixed suspension - mixed product removal (MSMPR) mixer operating at steady state. The influence of the operating parameters on the uranium peroxide agglomerates was studied in order to identify the agglomeration kernel. The method is based on the resolution of the population balance equation using the method of moments and the experimental particle size distributions. The results lead to a size-independent kernel directly proportional to the crystal growth rate. Under the stirring conditions studied, the agglomeration appears to be significantly reduced by mixing which results in a kernel inversely proportional to the average shear rate. The agglomeration kinetic law obtained in this study will be used for the process modelling in a further study. (authors)

  17. Study on the agglomeration kinetics of uranium peroxide

    International Nuclear Information System (INIS)

    Bertrand, M.; Mojica Rodriguez, L.A.; Muhr, H.; Plasari, E.; Auger, F.

    2016-01-01

    Considering the previous study dealing with thermodynamic and kinetic phenomena (nucleation and crystal growth) during the uranium peroxide precipitation, this work focuses on the agglomeration mechanism. It provides the results obtained from the experiments carried out in a mixed suspension - mixed product removal (MSMPR) mixer operating at steady state. The influence of the operating parameters on the uranium peroxide agglomerates was studied in order to identify the agglomeration kernel. The method is based on the resolution of the population balance equation using the method of moments and the experimental particle size distributions. The results lead to a size-independent kernel directly proportional to the crystal growth rate. Under the stirring conditions studied, the agglomeration appears to be significantly reduced by mixing which results in a kernel inversely proportional to the average shear rate. The agglomeration kinetic law obtained in this study will be used for the process modelling in a further study. (authors)

  18. Selected readings in chemical kinetics

    CERN Document Server

    Back, Margaret H

    2013-01-01

    Selected Readings in Chemical Kinetics covers excerpts from 12 papers in the field of general and gas-phase kinetics. The book discusses papers on the laws of connexion between the conditions of a chemical change and its amount; on the reaction velocity of the inversion of the cane sugar by acids; and the calculation in absolute measure of velocity constants and equilibrium constants in gaseous systems. The text then tackles papers on simple gas reactions; on the absolute rate of reactions in condensed phases; on the radiation theory of chemical action; and on the theory of unimolecular reacti

  19. Chemical kinetics and reaction dynamics

    CERN Document Server

    Houston, Paul L

    2006-01-01

    This text teaches the principles underlying modern chemical kinetics in a clear, direct fashion, using several examples to enhance basic understanding. It features solutions to selected problems, with separate sections and appendices that cover more technical applications.Each chapter is self-contained and features an introduction that identifies its basic goals, their significance, and a general plan for their achievement. This text's important aims are to demonstrate that the basic kinetic principles are essential to the solution of modern chemical problems, and to show how the underlying qu

  20. Chemical kinetics and combustion modeling

    Energy Technology Data Exchange (ETDEWEB)

    Miller, J.A. [Sandia National Laboratories, Livermore, CA (United States)

    1993-12-01

    The goal of this program is to gain qualitative insight into how pollutants are formed in combustion systems and to develop quantitative mathematical models to predict their formation rates. The approach is an integrated one, combining low-pressure flame experiments, chemical kinetics modeling, theory, and kinetics experiments to gain as clear a picture as possible of the process in question. These efforts are focused on problems involved with the nitrogen chemistry of combustion systems and on the formation of soot and PAH in flames.

  1. Deuteration kinetics of the graphene

    Energy Technology Data Exchange (ETDEWEB)

    Nefedov, Alexei; Woell, Christof [KIT, Leopoldshafen (Germany); Paris, Alessio; Calliari, Lucia [FBK-CMM, Trento (Italy); Verbitskiy, Nikolay [MSU, Moscow (Russian Federation); University of Vienna, Vienna (Austria); Wang, Ying; Irle, Stephan [Nagoya University, Nagoya (Japan); Fedorov, Alexander [IFW Dresden, Dresden (Germany); St. Petersburg University, St. Petersburg (Russian Federation); Haberer, Danny; Knupfer, Martin; Buechner, Bernd [IFW Dresden, Dresden (Germany); Oetzelt, Martin [BESSY II, Berlin (Germany); Petaccia, Luca [Elettra, Trieste (Italy); Usachov, Dmitry [St. Petersburg University, St. Petersburg (Russian Federation); Vyalikh, Denis [St. Petersburg University, St. Petersburg (Russian Federation); TU Dresden, Dresden (Germany); Sagdev, Hermann [MPI fuer Polymerforschung, Mainz (Germany); Yashina, Lada [MSU, Moscow (Russian Federation); Grueneis, Alexander [IFW Dresden, Dresden (Germany); University of Vienna, Vienna (Austria)

    2013-07-01

    The kinetics of the hydrogenation/deuteration reaction of graphene was studied by time-dependent x-ray photoemission spectroscopy (XPS). The graphene layer was then exposed to hydrogen or deuterium atomic gas beams, obtained by thermal cracking in a tungsten capillary at T=3000 K. After each step XPS of the C1s line was performed in order to measure H/C and D/C ratios. We have observed a strong kinetic isotope effect for the hydrogenation/deuteration reaction leading to substantially faster adsorption and higher maximum D/C ratios as compared to H/C (D/C 35% vs. H/C 25%).

  2. Vlasov simulations of Kinetic Alfven Waves at proton kinetic scales

    NARCIS (Netherlands)

    C.L. Vasconez; F. Valentini (Francesco); E. Camporeale (Enrico); P. Veltri

    2014-01-01

    htmlabstractKinetic Alfv ́en waves represent an important subject in space plasma physics, since they are thought to play a crucial role in the development of the turbulent energy cascade in the solar wind plasma at short wavelengths (of the order of the proton inertial length d p and beyond). A

  3. High resolution data acquisition

    Science.gov (United States)

    Thornton, Glenn W.; Fuller, Kenneth R.

    1993-01-01

    A high resolution event interval timing system measures short time intervals such as occur in high energy physics or laser ranging. Timing is provided from a clock (38) pulse train (37) and analog circuitry (44) for generating a triangular wave (46) synchronously with the pulse train (37). The triangular wave (46) has an amplitude and slope functionally related to the time elapsed during each clock pulse in the train. A converter (18, 32) forms a first digital value of the amplitude and slope of the triangle wave at the start of the event interval and a second digital value of the amplitude and slope of the triangle wave at the end of the event interval. A counter (26) counts the clock pulse train (37) during the interval to form a gross event interval time. A computer (52) then combines the gross event interval time and the first and second digital values to output a high resolution value for the event interval.

  4. High resolution photoelectron spectroscopy

    International Nuclear Information System (INIS)

    Arko, A.J.

    1988-01-01

    Photoelectron Spectroscopy (PES) covers a very broad range of measurements, disciplines, and interests. As the next generation light source, the FEL will result in improvements over the undulator that are larger than the undulater improvements over bending magnets. The combination of high flux and high inherent resolution will result in several orders of magnitude gain in signal to noise over measurements using synchrotron-based undulators. The latter still require monochromators. Their resolution is invariably strongly energy-dependent so that in the regions of interest for many experiments (h upsilon > 100 eV) they will not have a resolving power much over 1000. In order to study some of the interesting phenomena in actinides (heavy fermions e.g.) one would need resolving powers of 10 4 to 10 5 . These values are only reachable with the FEL

  5. Particle detector spatial resolution

    International Nuclear Information System (INIS)

    Perez-Mendez, V.

    1992-01-01

    Method and apparatus for producing separated columns of scintillation layer material, for use in detection of X-rays and high energy charged particles with improved spatial resolution is disclosed. A pattern of ridges or projections is formed on one surface of a substrate layer or in a thin polyimide layer, and the scintillation layer is grown at controlled temperature and growth rate on the ridge-containing material. The scintillation material preferentially forms cylinders or columns, separated by gaps conforming to the pattern of ridges, and these columns direct most of the light produced in the scintillation layer along individual columns for subsequent detection in a photodiode layer. The gaps may be filled with a light-absorbing material to further enhance the spatial resolution of the particle detector. 12 figs

  6. Elements of plasma kinetic theory

    International Nuclear Information System (INIS)

    Guasp, J.

    1976-01-01

    The physical foundations of plasma kinetic equations are exposed inside a series of seminars on plasma and fusion physics. The Vlasov and collisional equations with its application range have been discussed. The momenta equations for the macroscopic magnitudes and the more usual approximations have been obtained: two fluid equations for cold and warm plasmas, magnetohydrodynamic equations and the double-adiabatic theory. (author)

  7. Kinetic studies on leucite precursors

    Czech Academy of Sciences Publication Activity Database

    Mrázová, M.; Kloužková, A.; Kohoutková, Martina

    2009-01-01

    Roč. 7, č. 2 (2009), s. 205-210 ISSN 1895-1066 R&D Projects: GA MPO 2A-1TP1/063 Institutional research plan: CEZ:AV0Z40320502 Keywords : leucite * crystallization kinetics * hydrothermal Subject RIV: JH - Ceramics, Fire-Resistant Materials and Glass Impact factor: 1.065, year: 2009

  8. Some parameters of radionuclide kinetics

    International Nuclear Information System (INIS)

    Prokof'ev, O.N.; Smirnov, V.A.; Belen'kij, E.I.

    1978-01-01

    Numerical values of the rates of radionuclide absorption into, and elimination from, bovine organs were determined. Kinetic rate constants of radionuclides such as 89 Sr, 99 Mo, 131 I, 132 Tl, and 140 Be were calculated. The calculations were done for muscle, liver, and kidney

  9. Solving Simple Kinetics without Integrals

    Science.gov (United States)

    de la Pen~a, Lisandro Herna´ndez

    2016-01-01

    The solution of simple kinetic equations is analyzed without referencing any topic from differential equations or integral calculus. Guided by the physical meaning of the rate equation, a systematic procedure is used to generate an approximate solution that converges uniformly to the exact solution in the case of zero, first, and second order…

  10. Robustness Analysis of Kinetic Structures

    DEFF Research Database (Denmark)

    Kirkegaard, Poul Henning; Sørensen, John Dalsgaard

    2009-01-01

    Kinetic structures in architecture follows a new trend which is emerging in responsive architecture coined by Nicholas Negroponte when he proposed that architecture may benefit from the integration of computing power into built spaces and structures, and that better performing, more rational...

  11. Kinetics of Bio-Reactions

    DEFF Research Database (Denmark)

    Villadsen, John

    2015-01-01

    his chapter predicts the specific rates of reaction by means of a mathematical expression, the kinetics of the reaction. This expression can be derived through a mechanistic interpretation of an enzymatically catalyzed reaction, but it is essentially of empirical nature for cell reactions. The mo...

  12. Resonance transport and kinetic entropy

    International Nuclear Information System (INIS)

    Ivanov, Yu.B.; Knoll, J.; Voskresensky, D.N.

    2000-01-01

    We continue the description of the dynamics of unstable particles within the real-time formulation of nonequilibrium field theory initiated in a previous paper . There we suggest to use Baym's PHI-functional method in order to achieve approximation schemes with 'built in' consistency with respect to conservation laws and thermodynamics even in the case of particles with finite damping width. Starting from Kadanoff-Baym equations we discuss a consistent first order gradient approach to transport which preserves the PHI-derivable properties. The validity conditions for the resulting quantum four-phase-space kinetic theory are discussed under the perspective to treat particles with broad damping widths. This non-equilibrium dynamics naturally includes all those quantum features already inherent in the corresponding equilibrium limit (e.g. Matsubara formalism) at the same level of PHI-derivable approximation. Various collision-term diagrams are discussed including those of higher order which lead to memory effects. As an important novel part we derive a generalized nonequilibrium expression for the kinetic entropy flow, which includes contributions from fluctuations and mass-width effects. In special cases an H-theorem is derived implying that the entropy can only increase with time. Memory effects in the kinetic terms provide contributions to the kinetic entropy flow that in the equilibrium limit recover the famous bosonic type T 3 lnT correction to the specific heat in the case of Fermi liquids like Helium-3

  13. Total space in resolution

    Czech Academy of Sciences Publication Activity Database

    Bonacina, I.; Galesi, N.; Thapen, Neil

    2016-01-01

    Roč. 45, č. 5 (2016), s. 1894-1909 ISSN 0097-5397 R&D Projects: GA ČR GBP202/12/G061 EU Projects: European Commission(XE) 339691 - FEALORA Institutional support: RVO:67985840 Keywords : total space * resolution random CNFs * proof complexity Subject RIV: BA - General Mathematics Impact factor: 1.433, year: 2016 http://epubs.siam.org/doi/10.1137/15M1023269

  14. High resolution (transformers.

    Science.gov (United States)

    Garcia-Souto, Jose A; Lamela-Rivera, Horacio

    2006-10-16

    A novel fiber-optic interferometric sensor is presented for vibrations measurements and analysis. In this approach, it is shown applied to the vibrations of electrical structures within power transformers. A main feature of the sensor is that an unambiguous optical phase measurement is performed using the direct detection of the interferometer output, without external modulation, for a more compact and stable implementation. High resolution of the interferometric measurement is obtained with this technique (transformers are also highlighted.

  15. ALTERNATIVE DISPUTE RESOLUTION

    Directory of Open Access Journals (Sweden)

    Mihaela Irina IONESCU

    2016-05-01

    Full Text Available Alternative dispute resolution (ADR includes dispute resolution processes and techniques that act as a means for disagreeing parties to come to an agreement short of litigation. It is a collective term for the ways that parties can settle disputes, with (or without the help of a third party. Despite historic resistance to ADR by many popular parties and their advocates, ADR has gained widespread acceptance among both the general public and the legal profession in recent years. In fact, some courts now require some parties to resort to ADR of some type, before permitting the parties' cases to be tried. The rising popularity of ADR can be explained by the increasing caseload of traditional courts, the perception that ADR imposes fewer costs than litigation, a preference for confidentiality, and the desire of some parties to have greater control over the selection of the individual or individuals who will decide their dispute. Directive 2013/11/EU of the European Parliament and of the Council on alternative dispute resolution for consumer disputes and amending Regulation (EC No 2006/2004 and Directive 2009/22/EC (hereinafter „Directive 2013/11/EU” aims to ensure a high level of consumer protection and the proper functioning of the internal market by ensuring that complaints against traders can be submitted by consumers on a voluntary basis, to entities of alternative disputes which are independent, impartial, transparent, effective, simple,quick and fair. Directive 2013/11/EU establishes harmonized quality requirements for entities applying alternative dispute resolution procedure (hereinafter "ADR entity" to provide the same protection and the same rights of consumers in all Member States. Besides this, the present study is trying to present broadly how are all this trasposed in the romanian legislation.

  16. [Phylogenetic diversity and cold-adaptive hydrolytic enzymes of culturable psychrophilic bacteria associated with sea ice from high latitude ocean, Artic].

    Science.gov (United States)

    Yu, Yong; Li, Hui-Rong; Chen, Bo; Zeng, Yin-Xin; He, Jian-Feng

    2006-04-01

    showing 100% similarity each other are retrieved from the database, eleven from Antarctic seawater bacteria, three from Antarctic sea-ice bacteria, one from Spitzbergen sea-ice bacteria, two from Chukchi Sea sea-ice bacteria, two from Canadian Basin sea-ice bacteria (in this study) and one from uncultured bacterium clone PDA-OTU11 associated with the coral Pocillopora damicornis from the Great Barrier Reef. These may indicate that the physiological and geographic barriers appear to be permeable and some bacterial species can survive in different environment. The majority of the bacterial strains are able to secrete diversity cold-adaptive hydrolytic enzymes into the medium at 4 degrees C. The isolates that are able to degrade Tween-80, glutin, and starch account for, respectively, 62.6%, 51.4% and 40.5%.

  17. Turbulent kinetic energy balance measurements in the wake of a low-pressure turbine blade

    International Nuclear Information System (INIS)

    Sideridis, A.; Yakinthos, K.; Goulas, A.

    2011-01-01

    The turbulent kinetic energy budget in the wake generated by a high lift, low-pressure two-dimensional blade cascade of the T106 profile was investigated experimentally using hot-wire anemometry. The purpose of this study is to examine the transport mechanism of the turbulent kinetic energy and provide validation data for turbulence modeling. Point measurements were conducted on a high spatial resolution, two-dimensional grid that allowed precise derivative calculations. Positioning of the probe was achieved using a high accuracy traversing mechanism. The turbulent kinetic energy (TKE) convection, production, viscous diffusion and turbulent diffusion were all obtained directly from experimental measurements. Dissipation and pressure diffusion were calculated indirectly using techniques presented and validated by previous investigators. Results for all terms of the turbulent kinetic energy budget are presented and discussed in detail in the present work.

  18. Some Aspects of Extended Kinetic Equation

    Directory of Open Access Journals (Sweden)

    Dilip Kumar

    2015-09-01

    Full Text Available Motivated by the pathway model of Mathai introduced in 2005 [Linear Algebra and Its Applications, 396, 317–328] we extend the standard kinetic equations. Connection of the extended kinetic equation with fractional calculus operator is established. The solution of the general form of the fractional kinetic equation is obtained through Laplace transform. The results for the standard kinetic equation are obtained as the limiting case.

  19. Holographic kinetic k-essence model

    Energy Technology Data Exchange (ETDEWEB)

    Cruz, Norman [Departamento de Fisica, Facultad de Ciencia, Universidad de Santiago de Chile, Casilla 307, Santiago (Chile)], E-mail: ncruz@lauca.usach.cl; Gonzalez-Diaz, Pedro F.; Rozas-Fernandez, Alberto [Colina de los Chopos, Instituto de Fisica Fundamental, Consejo Superior de Investigaciones Cientificas, Serrano 121, 28006 Madrid (Spain)], E-mail: a.rozas@cfmac.csic.es; Sanchez, Guillermo [Departamento de Matematica y Ciencia de la Computacion, Facultad de Ciencia, Universidad de Santiago de Chile, Casilla 307, Santiago (Chile)], E-mail: gsanchez@usach.cl

    2009-08-31

    We consider a connection between the holographic dark energy density and the kinetic k-essence energy density in a flat FRW universe. With the choice c{>=}1, the holographic dark energy can be described by a kinetic k-essence scalar field in a certain way. In this Letter we show this kinetic k-essential description of the holographic dark energy with c{>=}1 and reconstruct the kinetic k-essence function F(X)

  20. Kinetic modelling of enzymatic starch hydrolysis

    NARCIS (Netherlands)

    Bednarska, K.A.

    2015-01-01

    Kinetic modelling of enzymatic starch hydrolysis – a summary

    K.A. Bednarska

    The dissertation entitled ‘Kinetic modelling of enzymatic starch hydrolysis’ describes the enzymatic hydrolysis and kinetic modelling of liquefaction and saccharification of wheat starch.

  1. High-Resolution Spectroscopy of Jet-Cooled 1,1 '-Diphenylethylene: Electronically Excited and Ionic States of a Prototypical Cross-Conjugated System

    NARCIS (Netherlands)

    Smolarek, S.; Vdovin, A.; Rijs, A.; van Walree, C. A.; Zgierski, M. Z.; Buma, W. J.

    2011-01-01

    The photophysics of a prototypical cross-conjugated pi-system, 1,1'-diphenylethylene, have been studied using high-resolution resonance enhanced multiphoton ionization excitation spectroscopy and zero kinetic energy photoelectron spectroscopy, in combination with advanced ab initio

  2. Bank Resolution in Europe

    DEFF Research Database (Denmark)

    N. Gordon, Jeffery; Ringe, Georg

    2015-01-01

    This chapter argues that the work of the European Banking Union remains incomplete in one important respect, the structural re-organization of large European financial firms that would make “resolution” of a systemically important financial firm a credible alternative to bail-out or some other sort...... of taxpayer assistance. A holding company structure in which the public parent holds unsecured term debt sufficient to cover losses at an operating financial subsidiary would facilitate a “Single Point of Entry” resolution procedure that would minimize knock-on effects from the failure of a systemically...

  3. Bank Resolution in Europe

    DEFF Research Database (Denmark)

    Gordon, Jeffrey N.; Ringe, Georg

    This chapter argues that the work of the European Banking Union remains incomplete in one important respect, the structural re-organization of large European financial firms that would make “resolution” of a systemically important financial firm a credible alternative to bail-out or some other sort...... of taxpayer assistance. A holding company structure in which the public parent holds unsecured term debt sufficient to cover losses at an operating financial subsidiary would facilitate a “Single Point of Entry” resolution procedure that would minimize knock-on effects from the failure of a systemically...

  4. High resolution backscattering instruments

    International Nuclear Information System (INIS)

    Coldea, R.

    2001-01-01

    The principle of operation of indirect-geometry time-of-flight spectrometers are presented, including the IRIS at the ISIS spallation neutron source. The key features that make those types of spectrometers ideally suited for low-energy spectroscopy are: high energy resolution over a wide dynamic range, and simultaneous measurement over a large momentum transfer range provided by the wide angular detector coverage. To exemplify these features are discussed of single-crystal experiments of the spin dynamics in the two-dimensional frustrated quantum magnet Cs 2 CuCl 4 . (R.P.)

  5. Failure Diameter Resolution Study

    Energy Technology Data Exchange (ETDEWEB)

    Menikoff, Ralph [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2017-12-19

    Previously the SURFplus reactive burn model was calibrated for the TATB based explosive PBX 9502. The calibration was based on fitting Pop plot data, the failure diameter and the limiting detonation speed, and curvature effect data for small curvature. The model failure diameter is determined utilizing 2-D simulations of an unconfined rate stick to find the minimum diameter for which a detonation wave propagates. Here we examine the effect of mesh resolution on an unconfined rate stick with a diameter (10mm) slightly greater than the measured failure diameter (8 to 9 mm).

  6. Conflict management and resolution.

    Science.gov (United States)

    Harolds, Jay; Wood, Beverly P

    2006-03-01

    When people work collaboratively, conflict will always arise. Understanding the nature and source of conflict and its progression and stages, resolution, and outcome is a vital aspect of leadership. Causes of conflict include the miscomprehension of communication, emotional issues, personal history, and values. When the difference is understood and the resultant behavior properly addressed, most conflict can be settled in a way that provides needed change in an organization and interrelationships. There are serious consequences of avoiding or mismanaging disagreements. Informed leaders can effectively prevent destructive conflicts.

  7. The super-resolution debate

    Science.gov (United States)

    Won, Rachel

    2018-05-01

    In the quest for nanoscopy with super-resolution, consensus from the imaging community is that super-resolution is not always needed and that scientists should choose an imaging technique based on their specific application.

  8. Resolution Enhancement of Multilook Imagery

    Energy Technology Data Exchange (ETDEWEB)

    Galbraith, Amy E. [Univ. of Arizona, Tucson, AZ (United States)

    2004-07-01

    This dissertation studies the feasibility of enhancing the spatial resolution of multi-look remotely-sensed imagery using an iterative resolution enhancement algorithm known as Projection Onto Convex Sets (POCS). A multi-angle satellite image modeling tool is implemented, and simulated multi-look imagery is formed to test the resolution enhancement algorithm. Experiments are done to determine the optimal con guration and number of multi-angle low-resolution images needed for a quantitative improvement in the spatial resolution of the high-resolution estimate. The important topic of aliasing is examined in the context of the POCS resolution enhancement algorithm performance. In addition, the extension of the method to multispectral sensor images is discussed and an example is shown using multispectral confocal fluorescence imaging microscope data. Finally, the remote sensing issues of atmospheric path radiance and directional reflectance variations are explored to determine their effect on the resolution enhancement performance.

  9. Imaging collagen type I fibrillogenesis with high spatiotemporal resolution

    International Nuclear Information System (INIS)

    Stamov, Dimitar R; Stock, Erik; Franz, Clemens M; Jähnke, Torsten; Haschke, Heiko

    2015-01-01

    Fibrillar collagens, such as collagen type I, belong to the most abundant extracellular matrix proteins and they have received much attention over the last five decades due to their large interactome, complex hierarchical structure and high mechanical stability. Nevertheless, the collagen self-assembly process is still incompletely understood. Determining the real-time kinetics of collagen type I formation is therefore pivotal for better understanding of collagen type I structure and function, but visualising the dynamic self-assembly process of collagen I on the molecular scale requires imaging techniques offering high spatiotemporal resolution. Fast and high-speed scanning atomic force microscopes (AFM) provide the means to study such processes on the timescale of seconds under near-physiological conditions. In this study we have applied fast AFM tip scanning to study the assembly kinetics of fibrillar collagen type I nanomatrices with a temporal resolution reaching eight seconds for a frame size of 500 nm. By modifying the buffer composition and pH value, the kinetics of collagen fibrillogenesis can be adjusted for optimal analysis by fast AFM scanning. We furthermore show that amplitude-modulation imaging can be successfully applied to extract additional structural information from collagen samples even at high scan rates. Fast AFM scanning with controlled amplitude modulation therefore provides a versatile platform for studying dynamic collagen self-assembly processes at high resolution. - Highlights: • Continuous non-invasive time-lapse investigation of collagen I fibrillogenesis in situ. • Imaging of collagen I self-assembly with high spatiotemporal resolution. • Application of setpoint modulation to study the hierarchical structure of collagen I. • Observing real-time formation of the D-banding pattern in collagen I

  10. Imaging collagen type I fibrillogenesis with high spatiotemporal resolution

    Energy Technology Data Exchange (ETDEWEB)

    Stamov, Dimitar R, E-mail: stamov@jpk.com [JPK Instruments AG, Bouchéstrasse 12, 12435 Berlin (Germany); Stock, Erik [JPK Instruments AG, Bouchéstrasse 12, 12435 Berlin (Germany); Franz, Clemens M [DFG-Center for Functional Nanostructures (CFN), Karlsruhe Institute of Technology (KIT), Wolfgang-Gaede-Strasse 1a, 76131 Karlsruhe (Germany); Jähnke, Torsten; Haschke, Heiko [JPK Instruments AG, Bouchéstrasse 12, 12435 Berlin (Germany)

    2015-02-15

    Fibrillar collagens, such as collagen type I, belong to the most abundant extracellular matrix proteins and they have received much attention over the last five decades due to their large interactome, complex hierarchical structure and high mechanical stability. Nevertheless, the collagen self-assembly process is still incompletely understood. Determining the real-time kinetics of collagen type I formation is therefore pivotal for better understanding of collagen type I structure and function, but visualising the dynamic self-assembly process of collagen I on the molecular scale requires imaging techniques offering high spatiotemporal resolution. Fast and high-speed scanning atomic force microscopes (AFM) provide the means to study such processes on the timescale of seconds under near-physiological conditions. In this study we have applied fast AFM tip scanning to study the assembly kinetics of fibrillar collagen type I nanomatrices with a temporal resolution reaching eight seconds for a frame size of 500 nm. By modifying the buffer composition and pH value, the kinetics of collagen fibrillogenesis can be adjusted for optimal analysis by fast AFM scanning. We furthermore show that amplitude-modulation imaging can be successfully applied to extract additional structural information from collagen samples even at high scan rates. Fast AFM scanning with controlled amplitude modulation therefore provides a versatile platform for studying dynamic collagen self-assembly processes at high resolution. - Highlights: • Continuous non-invasive time-lapse investigation of collagen I fibrillogenesis in situ. • Imaging of collagen I self-assembly with high spatiotemporal resolution. • Application of setpoint modulation to study the hierarchical structure of collagen I. • Observing real-time formation of the D-banding pattern in collagen I.

  11. Morphogenesis of Kinetic Reciprocal Frames

    DEFF Research Database (Denmark)

    Parigi, Dario; Sassone, Mario

    2011-01-01

    Kinetic structures in civil engineering and architecture gained considerable more attention in the very recent years as a practical solution to face time dependant performances. Realized projects are mostly bridges, retractable roofs, while in architecture the trend follows the category of intera......Kinetic structures in civil engineering and architecture gained considerable more attention in the very recent years as a practical solution to face time dependant performances. Realized projects are mostly bridges, retractable roofs, while in architecture the trend follows the category...... (RF) were studied in the past as a practical solution to span distances with shorter elements. Leonardo da Vinci discovered interesting RF patterns and studied three dimensional arch structures for bridges. RF are generally defined as structures that forms closed circuits of forces, and where elements...

  12. Kinetic approach to relativistic dissipation

    Science.gov (United States)

    Gabbana, A.; Mendoza, M.; Succi, S.; Tripiccione, R.

    2017-08-01

    Despite a long record of intense effort, the basic mechanisms by which dissipation emerges from the microscopic dynamics of a relativistic fluid still elude complete understanding. In particular, several details must still be finalized in the pathway from kinetic theory to hydrodynamics mainly in the derivation of the values of the transport coefficients. In this paper, we approach the problem by matching data from lattice-kinetic simulations with analytical predictions. Our numerical results provide neat evidence in favor of the Chapman-Enskog [The Mathematical Theory of Non-Uniform Gases, 3rd ed. (Cambridge University Press, Cambridge, U.K., 1970)] procedure as suggested by recent theoretical analyses along with qualitative hints at the basic reasons why the Chapman-Enskog expansion might be better suited than Grad's method [Commun. Pure Appl. Math. 2, 331 (1949), 10.1002/cpa.3160020403] to capture the emergence of dissipative effects in relativistic fluids.

  13. Kinetic theory of tearing instability

    International Nuclear Information System (INIS)

    Hazeltine, R.D.; Dobrott, D.; Wang, T.S.

    1975-01-01

    The guiding-center kinetic equation with Fokker-Planck collision term is used to study, in cylindrical geometry, a class of dissipative instabilities of which the classical tearing mode is an archetype. Variational solution of the kinetic equation obviates the use of an approximate Ohm's law or adiabatic assumption, as used in previous studies, and it provides a dispersive relation which is uniformly valid for any ratio of wave frequency to collision frequency. One result of using the rigorous collision operator is the prediction of a new instability. This instability, driven by the electron temperature gradient, is predicted to occur under the long mean-free path conditions of present tokamak experiments, and has significant features in common with the kink-like oscillations observed in such experiments

  14. Kinetics of cadmium hydroxide precipitation

    International Nuclear Information System (INIS)

    Patterson, J.W.; Marani, D.; Luo, B.; Swenson, P.

    1987-01-01

    This paper presents some preliminary results on the kinetics of Cd(OH)/sub 2/ precipitation, both in the absence and the presence of citric acid as an inhibiting agent. Batch and continuous stirred tank reactor (CSTR) precipitation studies are performed by mixing equal volumes of NaOH and Cd(NO/sub 3/)/sub 2/ solutions, in order to avoid localized supersaturation conditions. The rate of metal removal from the soluble phase is calculated from the mass balance for the CSTR precipitation tests. In addition, precipitation kinetics are studied in terms of nucleation and crystal growth rates, by means of a particle counter that allows a population balance analysis for the precipitation reactor at steady state conditions

  15. Art Engineering and Kinetic Art

    Directory of Open Access Journals (Sweden)

    Barış Yılmaz

    2014-12-01

    Full Text Available Performing an art, either by painting or by sculpturing, requires to be interdisciplinary. When an artist creates his/her work of art, the process he/she realizes is supported by different engineering disciplines. Therefore, especially modern artists need to understand engineering science and this results in transforming artists into engineers. Opportunities provided by technology and science enable artists to expand his/her vision and to improve his/her works. Especially kinetic art has become an approach that combines art with engineering. Kinetic art, which is nourished with varied disciplines, is an excellent example to prove that art is interdisciplinary and to show the relationship between artist/art and engineering.

  16. Modeling the isochronal crystallization kinetics

    International Nuclear Information System (INIS)

    Sahay, S.S.; Krishnan, Karthik

    2004-01-01

    The classical Johnson-Mehl-Avrami-Kolmogorov (JMAK) model, originally formulated for the isothermal condition, is often used in conjunction with additivity principle for modeling the non-isothermal crystallization kinetics. This approach at times results in significant differences between the model prediction and experimental data. In this article, a modification to this approach has been imposed via an additional functional relationship between the activation energy and heating rate. The methodology has been validated with experimental isochronal crystallization kinetic data in Se 71 Te 20 Sb 9 glass and Ge 20 Te 80 systems. It has been shown that the functional relationship between heating rate and activation energy, ascribed to the reduction in apparent activation energy due to increasing non-isothermality, provides better phenomenological description and therefore improves the prediction capability of the JMAK model under isochronal condition

  17. Muscular Oxygen Uptake Kinetics in Aged Adults.

    Science.gov (United States)

    Koschate, J; Drescher, U; Baum, K; Eichberg, S; Schiffer, T; Latsch, J; Brixius, K; Hoffmann, U

    2016-06-01

    Pulmonary oxygen uptake (V˙O2) kinetics and heart rate kinetics are influenced by age and fitness. Muscular V˙O2 kinetics can be estimated from heart rate and pulmonary V˙O2. In this study the applicability of a test using pseudo-random binary sequences in combination with a model to estimate muscular V˙O2 kinetics was tested. Muscular V˙O2 kinetics were expected to be faster than pulmonary V˙O2 kinetics, slowed in aged subjects and correlated with maximum V˙O2 and heart rate kinetics. 27 elderly subjects (73±3 years; 81.1±8.2 kg; 175±4.7 cm) participated. Cardiorespiratory kinetics were assessed using the maximum of cross-correlation functions, higher maxima implying faster kinetics. Muscular V˙O2 kinetics were faster than pulmonary V˙O2 kinetics (0.31±0.1 vs. 0.29±0.1 s; p=0.004). Heart rate kinetics were not correlated with muscular or pulmonary V˙O2 kinetics or maximum V˙O2. Muscular V˙O2 kinetics correlated with maximum V˙O2 (r=0.35; p=0.033). This suggests, that muscular V˙O2 kinetics are faster than estimates from pulmonary V˙O2 and related to maximum V˙O2 in aged subjects. In the future this experimental approach may help to characterize alterations in muscular V˙O2 under various conditions independent of motivation and maximal effort. © Georg Thieme Verlag KG Stuttgart · New York.

  18. Bumetanide kinetics in renal failure

    International Nuclear Information System (INIS)

    Pentikaeinen, P.J.P.; Pasternack, A.; Lampainen, E.; Neuvonen, P.J.; Penttilae, A.

    1985-01-01

    To study the effects of renal failure on bumetanide kinetics, the authors administered single intravenous doses of 1.0 mg/3.08 microCi 14 C-bumetanide to six healthy subjects and 22 patients with variable degrees of renal failure. The kinetics of 14 C-bumetanide and total 14 C were adequately described by a two-compartment open model in the control subjects and in the patients. The volume of the central compartment and the distribution t1/2 were of the same order in both groups, whereas the mean (+/- SE) volume at steady state was larger (22.1 +/- 1.6 and 16.9 +/- 1.0 L) and the elimination t1/2 was longer (1.9 +/- 0.2 and 1.4 +/- 0.1 hours) in patients with renal failure than in healthy controls. Bumetanide renal clearance was lower (10 +/- 3 and 90 +/- 13 ml/min) in patients than in subjects and correlated with creatinine clearance (r = 0.784) and log serum creatinine level (r = -0.843), whereas nonrenal clearance was significantly higher in the patients (153 +/- 14 and 99 +/- 6 ml/min). Bumetanide total plasma clearance did not significantly change. The non-protein-bound, free fraction of bumetanide was higher in patients and correlated with plasma albumin levels (r = -0.777). The kinetics of total 14 C showed similar but greater changes than those of 14C-bumetanide. Thus the most important changes in bumetanide kinetics in patients with renal failure are low renal clearance and a high free fraction, with a consequent increase in nonrenal clearance, volume of distribution, and elimination t1/2

  19. Production kinetics of zirconium tetrachloride

    International Nuclear Information System (INIS)

    Sudjoko, D.; Masduki, B.; Sunardjo; Sulistyo, B.

    1996-01-01

    This research was intended to study the kinetics of zirconium tetrachloride production. The process was carried out in semi continuous reactor, equipped with heater, temperature controller, sublimator and scrubber. The variables investigated were time, temperature and the pellet forming pressure. Within the range of variables studied, the expression of the process in the chemical reaction controller region and diffusion controller region were both presented. (author)

  20. On the kinetic energy density

    International Nuclear Information System (INIS)

    Lombard, R.J.; Mas, D.; Moszkowski, S.A.

    1991-01-01

    We discuss two expressions for the density of kinetic energy which differ by an integration by parts. Using the Wigner transform we shown that the arithmetic mean of these two terms is closely analogous to the classical value. Harmonic oscillator wavefunctions are used to illustrate the radial dependence of these expressions. We study the differences they induce through effective mass terms when performing self-consistent calculations. (author)

  1. Kinetics of UO2 sintering

    International Nuclear Information System (INIS)

    Ristic, M.M.

    1962-01-01

    Detailed conclusions related to the UO 2 sintering can be drawn from investigating the kinetics of the sintering process. This report gives an thorough analysis of the the data concerned with sintering available in the literature taking into account the Jander and Arrhenius laws. This analysis completes the study of influence of the O/U ratio and the atmosphere on the sintering. Results presented are fundamentals of future theoretical and experimental work related to characterisation of the UO 2 sintering process

  2. Automating the conflict resolution process

    Science.gov (United States)

    Wike, Jeffrey S.

    1991-01-01

    The purpose is to initiate a discussion of how the conflict resolution process at the Network Control Center can be made more efficient. Described here are how resource conflicts are currently resolved as well as the impacts of automating conflict resolution in the ATDRSS era. A variety of conflict resolution strategies are presented.

  3. Resolution of praziquantel.

    Directory of Open Access Journals (Sweden)

    Michael Woelfle

    2011-09-01

    Full Text Available BACKGROUND: Praziquantel remains the drug of choice for the worldwide treatment and control of schistosomiasis. The drug is synthesized and administered as a racemate. Use of the pure active enantiomer would be desirable since the inactive enantiomer is associated with side effects and is responsible for the extremely bitter taste of the pill. METHODOLOGY/PRINCIPAL FINDINGS: We have identified two resolution approaches toward the production of praziquantel as a single enantiomer. One approach starts with commercially available praziquantel and involves a hydrolysis to an intermediate amine, which is resolved with a derivative of tartaric acid. This method was discovered through an open collaboration on the internet. The second method, identified by a contract research organisation, employs a different intermediate that may be resolved with tartaric acid itself. CONCLUSIONS/SIGNIFICANCE: Both resolution procedures identified show promise for the large-scale, economically viable production of praziquantel as a single enantiomer for a low price. Additionally, they may be employed by laboratories for the production of smaller amounts of enantiopure drug for research purposes that should be useful in, for example, elucidation of the drug's mechanism of action.

  4. High resolution hadron calorimetry

    International Nuclear Information System (INIS)

    Wigmans, R.

    1987-01-01

    The components that contribute to the signal of a hadron calorimeter and the factors that affect its performance are discussed, concentrating on two aspects; energy resolution and signal linearity. Both are decisively dependent on the relative response to the electromagnetic and the non-electromagnetic shower components, the e/h signal ratio, which should be equal to 1.0 for optimal performance. The factors that determine the value of this ratio are examined. The calorimeter performance is crucially determined by its response to the abundantly present soft neutrons in the shower. The presence of a considerable fraction of hydrogen atoms in the active medium is essential for achieving the best possible results. Firstly, this allows one to tune e/h to the desired value by choosing the appropriate sampling fraction. And secondly, the efficient neutron detection via recoil protons in the readout medium itself reduces considerably the effect of fluctuations in binding energy losses at the nuclear level, which dominate the intrinsic energy resolution. Signal equalization, or compensation (e/h = 1.0) does not seem to be a property unique to 238 U, but can also be achieved with lead and probably even iron absorbers. 21 refs.; 19 figs

  5. KINETIC ALGORITHMS FOR HARBOUR MANAGEMENT

    Directory of Open Access Journals (Sweden)

    C. M. Gold

    2012-07-01

    Full Text Available Modern harbour management for a busy port needs to resolve a variety of simultaneous problems. Harbour traffic may be busy and the waterways congested, both by the major shipping and by the attendant harbour tugs. The harbour channel may be narrow and tortuous, and rapidly changing tides may require frequent course adjustments. Navigation aids must be clearly specified and immediately identifiable, in order to permit safe passage for the vessels. This requires a GIS with attributes not easily available with traditional products. The GeoVS system is a kinetic GIS with full three-dimensional visualisation, so that ships, bathymetry and landscape may be viewed in a form that is immediately understandable to both harbour pilots and the harbour authority. The system is kinetic because the data structures used to preserve the topological relationships between ships, seafloor and coastline are able to be maintained on a real-time basis, taking account of ship movement recorded on the compulsory AIS (Automatic Information System beacons. Maintenance of this real-time topology allows for easy detection of potential collisions, as well as real-time bathymetric estimations, necessary to prevent ship grounding in highly tidal environments. The system, based on previous research into kinetic Voronoi diagrams, as well as development of a completely new graphical engine, is now in commercial production, where its advantages over simpler twodimensional models without automatic collision and grounding detection are becoming evident. Other applications are readily envisaged, and will be addressed in the near future.

  6. Oxidation kinetics of corium pool

    Energy Technology Data Exchange (ETDEWEB)

    Sulatsky, A.A., E-mail: andrei314@mail.ru [Alexandrov Research Institute of Technologies (NITI), Sosnovy Bor (Russian Federation); Smirnov, S.A. [D.V. Efremov Scientific Research Institute of Electrophysical Apparatus (NIIEFA), St. Petersburg (Russian Federation); Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Vitol, S.A.; Kotova, S.Yu. [Alexandrov Research Institute of Technologies (NITI), Sosnovy Bor (Russian Federation); Fischer, M.; Hellmann, S. [AREVA NP GmbH, Erlangen (Germany); Tromm, W.; Miassoedov, A. [Forschungzentrum Karlsruhe (FZK), Karlsruhe (Germany); Bottomley, D. [EUROPÄISCHE KOMMISSION, Joint Research Centre Institut für Transurane (ITU), Karlsruhe (Germany); Piluso, P. [CEA Cadarache-DEN/DTN/STRI, St.Paul-lez-Durance (France); Barrachin, M. [Institut de Radioprotection et Sûreté Nucléaire, St.Paul-lez-Durance (France)

    2013-09-15

    Highlights: • The analysis of experimental data on molten corium oxidation was been carried out. • The analysis has revealed the main factors influencing the oxidation kinetics. • The analysis was used for developing a qualitative analytical model. • The numerical modeling has confirmed the results of experimental data analysis. -- Abstract: Experimental, theoretical and numerical studies of oxidation kinetics of an open surface corium pool have been reported. The experiments have been carried out within OECD MASCA program and ISTC METCOR, METCOR-P and EVAN projects. It has been shown that the melt oxidation is controlled by an oxidant supply to the melt free surface from the atmosphere, not by the reducer supply from the melt. The project experiments have not detected any input of the zirconium oxidation kinetics into the process chemistry. The completed analysis puts forward a simple analytical model, which gives an explanation of the main features of melt oxidation process. The numerical modeling results are in good agreement with experimental data and theoretical considerations.

  7. Oxidation kinetics of corium pool

    International Nuclear Information System (INIS)

    Sulatsky, A.A.; Smirnov, S.A.; Granovsky, V.S.; Khabensky, V.B.; Krushinov, E.V.; Vitol, S.A.; Kotova, S.Yu.; Fischer, M.; Hellmann, S.; Tromm, W.; Miassoedov, A.; Bottomley, D.; Piluso, P.; Barrachin, M.

    2013-01-01

    Highlights: • The analysis of experimental data on molten corium oxidation was been carried out. • The analysis has revealed the main factors influencing the oxidation kinetics. • The analysis was used for developing a qualitative analytical model. • The numerical modeling has confirmed the results of experimental data analysis. -- Abstract: Experimental, theoretical and numerical studies of oxidation kinetics of an open surface corium pool have been reported. The experiments have been carried out within OECD MASCA program and ISTC METCOR, METCOR-P and EVAN projects. It has been shown that the melt oxidation is controlled by an oxidant supply to the melt free surface from the atmosphere, not by the reducer supply from the melt. The project experiments have not detected any input of the zirconium oxidation kinetics into the process chemistry. The completed analysis puts forward a simple analytical model, which gives an explanation of the main features of melt oxidation process. The numerical modeling results are in good agreement with experimental data and theoretical considerations

  8. Aluminum corrosion product release kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Edwards, Matt, E-mail: Matthew.Edwards@cnl.ca; Semmler, Jaleh; Guzonas, Dave; Chen, Hui Qun; Toor, Arshad; Hoendermis, Seanna

    2015-07-15

    Highlights: • Release of Al corrosion product was measured in simulated post-LOCA sump solutions. • Increased boron was found to enhance Al release kinetics at similar pH. • Models of Al release as functions of time, temperature, and pH were developed. - Abstract: The kinetics of aluminum corrosion product release was examined in solutions representative of post-LOCA sump water for both pressurized water and pressurized heavy-water reactors. Coupons of AA 6061 T6 were exposed to solutions in the pH 7–11 range at 40, 60, 90 and 130 °C. Solution samples were analyzed by inductively coupled plasma atomic emission spectroscopy, and coupon samples were analyzed by secondary ion mass spectrometry. The results show a distinct “boron effect” on the release kinetics, expected to be caused by an increase in the solubility of the aluminum corrosion products. New models were developed to describe both sets of data as functions of temperature, time, and pH (where applicable)

  9. The eddy kinetic energy budget in the Red Sea

    KAUST Repository

    Zhan, Peng

    2016-06-09

    The budget of eddy kinetic energy (EKE) in the Red Sea, including the sources, redistributions and sink, is examined using a high-resolution eddy-resolving ocean circulation model. A pronounced seasonally varying EKE is identified, with its maximum intensity occurring in winter, and the strongest EKE is captured mainly in the central and northern basins within the upper 200 m. Eddies acquire kinetic energy from conversion of eddy available potential energy (EPE), from transfer of mean kinetic energy (MKE), and from direct generation due to time-varying (turbulent) wind stress, the first of which contributes predominantly to the majority of the EKE. The EPE-to-EKE conversion occurs almost in the entire basin, while the MKE-to-EKE transfer appears mainly along the shelf boundary of the basin (200 miso-bath) where high horizontal shear interacts with topography. The EKE generated by the turbulent wind stress is relatively small and limited to the southern basin. All these processes are intensified during winter, when the rate of energy conversion is about four to five times larger than that in summer. The EKE is redistributed by the vertical and horizontal divergence of energy flux and the advection of the mean flow. As a main sink of EKE, dissipation processes is ubiquitously found in the basin. The seasonal variability of these energy conversion terms can explain the significant seasonality of eddy activities in the Red Sea. This article is protected by copyright. All rights reserved.

  10. Modelling reveals kinetic advantages of co-transcriptional splicing.

    Directory of Open Access Journals (Sweden)

    Stuart Aitken

    2011-10-01

    Full Text Available Messenger RNA splicing is an essential and complex process for the removal of intron sequences. Whereas the composition of the splicing machinery is mostly known, the kinetics of splicing, the catalytic activity of splicing factors and the interdependency of transcription, splicing and mRNA 3' end formation are less well understood. We propose a stochastic model of splicing kinetics that explains data obtained from high-resolution kinetic analyses of transcription, splicing and 3' end formation during induction of an intron-containing reporter gene in budding yeast. Modelling reveals co-transcriptional splicing to be the most probable and most efficient splicing pathway for the reporter transcripts, due in part to a positive feedback mechanism for co-transcriptional second step splicing. Model comparison is used to assess the alternative representations of reactions. Modelling also indicates the functional coupling of transcription and splicing, because both the rate of initiation of transcription and the probability that step one of splicing occurs co-transcriptionally are reduced, when the second step of splicing is abolished in a mutant reporter.

  11. Modelling reveals kinetic advantages of co-transcriptional splicing.

    Science.gov (United States)

    Aitken, Stuart; Alexander, Ross D; Beggs, Jean D

    2011-10-01

    Messenger RNA splicing is an essential and complex process for the removal of intron sequences. Whereas the composition of the splicing machinery is mostly known, the kinetics of splicing, the catalytic activity of splicing factors and the interdependency of transcription, splicing and mRNA 3' end formation are less well understood. We propose a stochastic model of splicing kinetics that explains data obtained from high-resolution kinetic analyses of transcription, splicing and 3' end formation during induction of an intron-containing reporter gene in budding yeast. Modelling reveals co-transcriptional splicing to be the most probable and most efficient splicing pathway for the reporter transcripts, due in part to a positive feedback mechanism for co-transcriptional second step splicing. Model comparison is used to assess the alternative representations of reactions. Modelling also indicates the functional coupling of transcription and splicing, because both the rate of initiation of transcription and the probability that step one of splicing occurs co-transcriptionally are reduced, when the second step of splicing is abolished in a mutant reporter.

  12. Single Molecule Kinetics of ENTH Binding to Lipid Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Rozovsky, Sharon [Univ. of Delaware, Newark, DE (United States); Forstner, Martin B. [Syracuse Univ., NY (United States); Sondermann, Holger [Cornell Univ., Ithaca, NY (United States); Groves, Jay T. [Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

    2012-04-03

    Transient recruitment of proteins to membranes is a fundamental mechanism by which the cell exerts spatial and temporal control over proteins’ localization and interactions. Thus, the specificity and the kinetics of peripheral proteins’ membrane residence are an attribute of their function. In this article, we describe the membrane interactions of the interfacial epsin N-terminal homology (ENTH) domain with its target lipid phosphatidylinositol (4,5)-bisphosphate (PtdIns(4,5)P2). The direct visualization and quantification of interactions of single ENTH molecules with supported lipid bilayers is achieved using total internal reflection fluorescence microscopy (TIRFM) with a time resolution of 13 ms. This enables the recording of the kinetic behavior of ENTH interacting with membranes with physiologically relevant concentrations of PtdIns(4,5)P2 despite the low effective binding affinity. Subsequent single fluorophore tracking permits us to build up distributions of residence times and to measure ENTH dissociation rates as a function of membrane composition. In addition, due to the high time resolution, we are able to resolve details of the motion of ENTH associated with a simple, homogeneous membrane. In this case ENTH’s diffusive transport appears to be the result of at least three different diffusion processes.

  13. High Time Resolution Astrophysics

    CERN Document Server

    Phelan, Don; Shearer, Andrew

    2008-01-01

    High Time Resolution Astrophysics (HTRA) is an important new window to the universe and a vital tool in understanding a range of phenomena from diverse objects and radiative processes. This importance is demonstrated in this volume with the description of a number of topics in astrophysics, including quantum optics, cataclysmic variables, pulsars, X-ray binaries and stellar pulsations to name a few. Underlining this science foundation, technological developments in both instrumentation and detectors are described. These instruments and detectors combined cover a wide range of timescales and can measure fluxes, spectra and polarisation. These advances make it possible for HTRA to make a big contribution to our understanding of the Universe in the next decade.

  14. Lexical ambiguity resolution

    Energy Technology Data Exchange (ETDEWEB)

    Small, S.; Cottrell, G.; Tanenhaus, M.

    1987-01-01

    This book collects much of the best research currently available on the problem of lexical ambiguity resolution in the processing of human language. When taken out of context, sentences are usually ambiguous. When actually uttered in a dialogue or written in text, these same sentences often have unique interpretations. The inherent ambiguity of isolated sentences, becomes obvious in the attempt to write a computer program to understand them. Different views have emerged on the nature of context and the mechanisms by which it directs unambiguous understanding of words and sentences. These perspectives are represented and discussed. Eighteen original papers from a valuable source book for cognitive scientists in AI, psycholinguistics, neuropsychology, or theoretical linguistics.

  15. High resolution ultrasonic densitometer

    International Nuclear Information System (INIS)

    Dress, W.B.

    1983-01-01

    The velocity of torsional stress pulses in an ultrasonic waveguide of non-circular cross section is affected by the temperature and density of the surrounding medium. Measurement of the transit times of acoustic echoes from the ends of a sensor section are interpreted as level, density, and temperature of the fluid environment surrounding that section. This paper examines methods of making these measurements to obtain high resolution, temperature-corrected absolute and relative density and level determinations of the fluid. Possible applications include on-line process monitoring, a hand-held density probe for battery charge state indication, and precise inventory control for such diverse fluids as uranium salt solutions in accountability storage and gasoline in service station storage tanks

  16. Nonlinear Kinetics on Lattices Based on the Kinetic Interaction Principle

    Directory of Open Access Journals (Sweden)

    Giorgio Kaniadakis

    2018-06-01

    Full Text Available Master equations define the dynamics that govern the time evolution of various physical processes on lattices. In the continuum limit, master equations lead to Fokker–Planck partial differential equations that represent the dynamics of physical systems in continuous spaces. Over the last few decades, nonlinear Fokker–Planck equations have become very popular in condensed matter physics and in statistical physics. Numerical solutions of these equations require the use of discretization schemes. However, the discrete evolution equation obtained by the discretization of a Fokker–Planck partial differential equation depends on the specific discretization scheme. In general, the discretized form is different from the master equation that has generated the respective Fokker–Planck equation in the continuum limit. Therefore, the knowledge of the master equation associated with a given Fokker–Planck equation is extremely important for the correct numerical integration of the latter, since it provides a unique, physically motivated discretization scheme. This paper shows that the Kinetic Interaction Principle (KIP that governs the particle kinetics of many body systems, introduced in G. Kaniadakis, Physica A 296, 405 (2001, univocally defines a very simple master equation that in the continuum limit yields the nonlinear Fokker–Planck equation in its most general form.

  17. A kinetics database and scripts for PHREEQC

    Science.gov (United States)

    Hu, B.; Zhang, Y.; Teng, Y.; Zhu, C.

    2017-12-01

    Kinetics of geochemical reactions has been increasingly used in numerical models to simulate coupled flow, mass transport, and chemical reactions. However, the kinetic data are scattered in the literature. To assemble a kinetic dataset for a modeling project is an intimidating task for most. In order to facilitate the application of kinetics in geochemical modeling, we assembled kinetics parameters into a database for the geochemical simulation program, PHREEQC (version 3.0). Kinetics data were collected from the literature. Our database includes kinetic data for over 70 minerals. The rate equations are also programmed into scripts with the Basic language. Using the new kinetic database, we simulated reaction path during the albite dissolution process using various rate equations in the literature. The simulation results with three different rate equations gave difference reaction paths at different time scale. Another application involves a coupled reactive transport model simulating the advancement of an acid plume in an acid mine drainage site associated with Bear Creek Uranium tailings pond. Geochemical reactions including calcite, gypsum, and illite were simulated with PHREEQC using the new kinetic database. The simulation results successfully demonstrated the utility of new kinetic database.

  18. Understanding Yield Anomalies in ICF Implosions via Fully Kinetic Simulations

    Science.gov (United States)

    Taitano, William

    2017-10-01

    In the quest towards ICF ignition, plasma kinetic effects are among prime candidates for explaining some significant discrepancies between experimental observations and rad-hydro simulations. To assess their importance, high-fidelity fully kinetic simulations of ICF capsule implosions are needed. Owing to the extremely multi-scale nature of the problem, kinetic codes have to overcome nontrivial numerical and algorithmic challenges, and very few options are currently available. Here, we present resolutions of some long-standing yield discrepancy conundrums using a novel, LANL-developed, 1D-2V Vlasov-Fokker-Planck code iFP. iFP possesses an unprecedented fidelity and features fully implicit time-stepping, exact mass, momentum, and energy conservation, and optimal grid adaptation in phase space, all of which are critically important for ensuring long-time numerical accuracy of the implosion simulations. Specifically, we concentrate on several anomalous yield degradation instances observed in Omega campaigns, with the so-called ``Rygg effect'', or an anomalous yield scaling with the fuel composition, being a prime example. Understanding the physical mechanisms responsible for such degradations in non-ignition-grade Omega experiments is of great interest, as such experiments are often used for platform and diagnostic development, which are then used in ignition-grade experiments on NIF. In the case of Rygg's experiments, effects of a kinetic stratification of fuel ions on the yield have been previously proposed as the anomaly explanation, studied with a kinetic code FPION, and found unimportant. We have revisited this issue with iFP and obtained excellent yield-over-clean agreement with the original Rygg results, and several subsequent experiments. This validates iFP and confirms that the kinetic fuel stratification is indeed at the root of the observed yield degradation. This work was sponsored by the Metropolis Postdoctoral Fellowship, LDRD office, Thermonuclear Burn

  19. Kinetic Control of Intralayer Cobalt Coordination in Layered Hydroxides: CoxoctCoxtet(OH)2(Cl)x(H2O)n

    International Nuclear Information System (INIS)

    Neilson, James R.; Schwenzer, Birgit; Seshadri, Ram; Morse, Daniel E.

    2009-01-01

    We report the synthesis and characterization of new structural variants of the isotypic compound with the generic chemical formula, Co 1-0.5x oct Co x tet (OH) 2 (Cl) x (H 2 O) n , all modifications of an α-Co(OH) 2 lattice. We show that the occupancy of tetrahedrally coordinated cobalt sites and associated chloride ligands, x, is modulated by the rate of formation of the respective layered hydroxide salts from kinetically controlled aqueous hydrolysis at an air-water interface. This new level of structural control is uniquely enabled by the slow diffusion of a hydrolytic catalyst, a simple technique. Independent structural characterizations of the compounds separately describe various attributes of the materials on different length scales, revealing details hidden by the disordered average structures. The precise control over the population of distinct octahedrally and tetrahedrally coordinated cobalt ions in the lattice provides a gentle, generic method for modulating the coordination geometry of cobalt in the material without disturbing the lattice or using additional reagents. A mechanism is proposed to reconcile the observation of the kinetic control of the structure with competing interactions during the initial stages of hydrolysis and condensation.

  20. Thermodynamic basis for cluster kinetics

    DEFF Research Database (Denmark)

    Hu, Lina; Bian, Xiufang; Qin, Xubo

    2006-01-01

    Due to the inaccessibility of the supercooled region of marginal metallic glasses (MMGs) within the experimental time window, we study the cluster kinetics above the liquidus temperature, Tl, to acquire information on the fragility of the MMG systems. Thermodynamic basis for the stability...... of locally ordered structure in the MMG liquids is discussed in terms of the two-order-parameter model. It is found that the Arrhenius activation energy of clusters, h, is proportional to the chemical mixing enthalpy of alloys, Hchem. Fragility of the MMG forming liquids can be described by the ratio...

  1. Kinetics of heterogeneous catalytic reactions

    CERN Document Server

    Boudart, Michel

    2014-01-01

    This book is a critical account of the principles of the kinetics of heterogeneous catalytic reactions in the light of recent developments in surface science and catalysis science. Originally published in 1984. The Princeton Legacy Library uses the latest print-on-demand technology to again make available previously out-of-print books from the distinguished backlist of Princeton University Press. These paperback editions preserve the original texts of these important books while presenting them in durable paperback editions. The goal of the Princeton Legacy Library is to vastly increase acc

  2. Kinetic equations with pairing correlations

    International Nuclear Information System (INIS)

    Fauser, R.

    1995-12-01

    The Gorkov equations are derived for a general non-equilibrium system. The Gorkov factorization is generalized by the cumulant expansion of the 2-particle correlation and by a generalized Wick theorem in the case of a perturbation expansion. A stationary solution for the Green functions in the Schwinger-Keldysh formalism is presented taking into account pairing correlations. Especially the effects of collisional broadening on the spectral functions and Green functions is discussed. Kinetic equations are derived in the quasi-particle approximation and in the case of particles with width. Explicit expressions for the self-energies are given. (orig.)

  3. Kinetic theory of radiation effects

    International Nuclear Information System (INIS)

    Mansur, L.K.

    1987-01-01

    To help achieve the quantitative and mechanistic understanding of these processes, the kinetic theory of radiation effects has been developed in the DOE basic energy sciences radiation effects and fusion reactor materials programs, as well as in corresponding efforts in other countries. This discipline grapples with a very wide range of phenomena and draws on numerous sub-fields of theory such as defect physics, diffusion, elasticity, chemical reaction rates, phase transformations and thermodynamics. The theory is cast in a mathematical framework of continuum dynamics. Issues particularly relevant to the present inquiry can be viewed from the standpoints of applications of the theory and areas requiring further progress

  4. Addressing the Recalcitrance of Cellulose Degradation through Cellulase Discovery, Nano-scale Elucidation of Molecular Mechanisms, and Kinetic Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Walker, Larry P., Bergstrom, Gary; Corgie, Stephane; Craighead, Harold; Gibson, Donna; Wilson, David

    2011-06-13

    This research project was designed to play a vital role in the development of low cost sugars from cellulosic biomass and contributing to the national effort to displace fossil fuel usage in the USA transportation sector. The goal was to expand the portfolio of cell wall degrading enzymes through innovative research at the nano-scale level, prospecting for novel cellulases and building a kinetic framework for the development of more effective enzymatic conversion processes. More precisely, the goal was to elucidate the molecular mechanisms for some cellulases that are very familiar to members of our research team and to investigate what we hope are novel cellulases or new enzyme combinations from the world of plant pathogenic fungi and bacteria. Hydrolytic activities of various cellulases and cellulase cocktails were monitored at the nanoscale of cellulose fibrils and the microscale of pretreated cellulose particles, and we integrated this insight into a heterogeneous reaction framework. The over-riding approach for this research program was the application of innovative and cutting edge optical and high-throughput screening and analysis techniques for observing how cellulases hydrolyze real substrates.

  5. Environmental Systems Conflict Resolution

    Science.gov (United States)

    Hipel, K. W.

    2017-12-01

    The Graph Model for Conflict Resolution (GMCR) is applied to a real-life groundwater contamination dispute to demonstrate how one can realistically model and analyze the controversy in order to obtain an enhanced understanding and strategic insights for permitting one to make informed decisions. This highly divisive conflict is utilized to explain a rich range of inherent capabilities of GMCR, as well as worthwhile avenues for extensions, which make GMCR a truly powerful decision technology for addressing challenging conflict situations. For instance, a flexible preference elicitation method called option prioritization can be employed to obtain the relative preferences of each decision maker (DM) in the dispute over the states or scenarios which can occur, based upon preference statements regarding the options or courses of actions available to the DMs. Solution concepts, reflecting the way a chess player thinks in terms of moves and counter-moves, are defined to mirror the ways humans may behave under conflict, varying from short to long term thinking. After ascertaining the best outcome that a DM can achieve on his or her own in a conflict, coalition analysis algorithms are available to check if a DM can fare even better via cooperating with others. The ability of GMCR to take into account emotions, strength of preference, attitudes, misunderstandings (referred to as hypergames), and uncertain preferences (unknown, fuzzy, grey and probabilistic) greatly broadens its scope of applicability. Techniques for tracing how a conflict can evolve over time from a status quo state to a final specified outcome, as well as how to handle hierarchical structures, such as when a central government interacts with its provinces or states, further enforces the comprehensive nature of GMCR. Within ongoing conflict research mimicking how physical systems are analyzed, methods for inverse engineering of preferences are explained for determining the preferences required by one or

  6. Kinetic Control of Aqueous Hydrolysis: Modulating Structure/Property Relationships in Inorganic Crystals

    Science.gov (United States)

    Neilson, James R.

    2011-12-01

    A grand challenge in materials science and chemistry revolves around the preparation of materials with desired properties by controlling structure on multiple length scales. Biology approaches this challenge by evolving tactics to transform soluble precursors into materials and composites with macro-scale and atomic precision. Studies of biomineralization in siliceous sponges led to the discovery of slow, catalytic hydrolysis of molecular precursors in the biogenesis of silica skeletal elements with well defined micro- and nano-scale architectures. However, the role of aqueous hydrolysis in the limit of kinetic control is not well understood; this allows us to form a central hypothesis: that the kinetics of hydrolysis modulate the structures of materials and their properties. As a model system, the diffusion of a simple hydrolytic catalyst (such as ammonia) across an air-water interface into a metal salt solution reproduces some aspects of the chemistry found in biomineralization, namely kinetic and vectorial control. Variation of the catalyst concentration modulates the hydrolysis rate, and thus alters the resulting structure of the inorganic crystals. Using aqueous solutions of cobalt(II) chloride, each product (cobalt hydroxide chloride) forms with a unique composition, despite being prepared from identical mother liquors. Synchrotron X-ray total scattering methods are needed to locate the atomic positions in the material, which are not aptly described by a traditional crystallographic unit cell due to structural disorder. Detailed definition of the structure confirms that the hydrolysis conditions systematically modulate the arrangement of atoms in the lattice. This tightly coupled control of crystal formation and knowledge of local and average structures of these materials provides insight into the unusual magnetic properties of these cobalt hydroxides. The compounds studied show significant and open magnetization loops with little variation with composition

  7. Particle growth kinetics over the Amazon rainforest

    Science.gov (United States)

    Pinterich, T.; Andreae, M. O.; Artaxo, P.; Kuang, C.; Longo, K.; Machado, L.; Manzi, A. O.; Martin, S. T.; Mei, F.; Pöhlker, C.; Pöhlker, M. L.; Poeschl, U.; Shilling, J. E.; Shiraiwa, M.; Tomlinson, J. M.; Zaveri, R. A.; Wang, J.

    2016-12-01

    Aerosol particles larger than 100 nm play a key role in global climate by acting as cloud condensation nuclei (CCN). Most of these particles, originated from new particle formation or directly emitted into the atmospheric, are initially too small to serve as CCN. These small particles grow to CCN size mainly through condensation of secondary species. In one extreme, the growth is dictated by kinetic condensation of very low-volatility compounds, favoring the growth of the smallest particles; in the other extreme, the process is driven by Raoult's law-based equilibrium partitioning of semi-volatile organic compound, favoring the growth of larger particles. These two mechanisms can lead to very different production rates of CCN. The growth of particles depends on a number of parameters, including the volatility of condensing species, particle phase, and diffusivity inside the particles, and this process is not well understood in part due to lack of ambient data. Here we examine atmospheric particle growth using high-resolution size distributions measured onboard the DOE G-1 aircraft during GoAmazon campaign, which took place from January 2014 to December 2015 near Manaus, Brazil, a city surrounded by natural forest for over 1000 km in every direction. City plumes are clearly identified by the strong enhancement of nucleation and Aitken mode particle concentrations over the clean background. As the plume traveled downwind, particle growth was observed, and is attributed to condensation of secondary species and coagulation (Fig.1). Observed aerosol growth is modeled using MOSAIC (Model for Simulating Aerosol Interactions and Chemistry), which dynamically partitions multiple compounds to all particle size bins by taking into account compound volatility, gas-phase diffusion, interfacial mass accommodation, particle-phase diffusion, and particle-phase reaction. The results from both wet and dry seasons will be discussed.

  8. A kinetic model for hydrodesulfurisation

    Energy Technology Data Exchange (ETDEWEB)

    Sau, M.; Narasimhan, C.S.L.; Verma, R.P. [Indian Oil Corporation Limited, Research and Development Centre, Faridabad (India)

    1997-07-01

    Due to stringent environmental considerations and related insistence on low sulfur fuels, hydrodesulfurisation has emerged as an important component of any refining scheme globally. The process is used ranging from Naphta/Kerosine hydrotreating to heavy oil hydrotreating. Processes such as Deep gas oil desulfurisation aiming at reduction of sulfur levels to less than 500 ppm have emerged as major players in the scenario. Hydrodesulfurisation (HDS) involves parallel desulfurisation of different organo-sulfur compounds present in the complex petroleum mixtures. In order to design, monitor, optimise and control the HDS reactor, it is necessary to have a detailed, yet simple model which follows the reaction chemistry accurately. In the present paper, a kinetic model is presented for HDS using continuum theory of lumping. The sulfur distribution in the reaction mixture is treated as continuum and parallel reaction networks are devised for kinetic modelling using continuum theory of lumping approach. The model based on the above approach follows the HDS chemistry reasonably well and hence the model parameters are almost feed invariant. Methods are also devised to incorporate heat and pressure effects into the model. The model has been validated based on commercial kero-HDS data. It is found that the model predictions agree with the experimental/commercial data. 17 refs.

  9. Conformational kinetics of aliphatic tails

    Science.gov (United States)

    Ferrarini, Alberta; Moro, Giorgio; Nordio, Pier Luigi

    The master equation describing the random walk between sites identified with the stable conformers of a chain molecule, represents the extension to the time domain of the Rotational Isomeric State model. The asymptotic analysis of the multidimensional diffusion equation in the continuous torsional variables subjected to the configurational potential, provides a rigorous justification for the discrete models, and it supplies, without resorting to phenomenological parameters, molecular definitions of the kinetic rates for the conformational transitions occurring at each segment of the chain. The coupling between the torsional variables is fully taken into account, giving rise to cooperative effects. A complete calculation of the specific correlation functions which describe the time evolution of the angular functions probed by N.M.R. and dielectric relaxation measurements, has been performed for alkyl chains attached to a massive core. The resulting behaviour has been compared with the decay of trans and gauche populations of specific bonds, expressed in terms of suitable correlation functions whose time integrals lead quite naturally to the definition of effective kinetic constants for the conformational transitions.

  10. Blood-organ transfer kinetics

    International Nuclear Information System (INIS)

    Skrable, K.W.; Chabot, G.E.; French, C.S.; Wrenn, M.E.; Lipsztein, J.; Sasso, T.L.; Durbin, P.W.

    1980-01-01

    Exact and approximate kinetics equations relating to the transfer and elimination of radionuclides from the blood and various organs in the body are presented. These expressions may be used to estimate the instantaneous activity or the total number of disintegrations of a radionuclide in the blood or various organs of reference in the body, hence, also the respective dose rates and doses. The exact kinetics equations may be used to relate measurements of radionuclides in excreta to burdens in the body. They do give better results for exposure intervals long compared to the effective mean lives of the radionuclide in the various organs of reference, and they yield the exact steady state expressions. Fortunately, this condition is often satisfied for the relatively long standard exposure interval of 50 years that is applied to occupational exposure. In addition, the steady state expressions may be used along with metabolic data of the distribution of elements in the body, diet and excreta to estimate values of the rate constants used in both the exact and approximate expressions. A comparison of the exact and approximate expressions is given for the uranium metabolic model of Wrenn et al. and a comparison is made with current ICRP models. (author)

  11. Combustion kinetics and reaction pathways

    Energy Technology Data Exchange (ETDEWEB)

    Klemm, R.B.; Sutherland, J.W. [Brookhaven National Laboratory, Upton, NY (United States)

    1993-12-01

    This project is focused on the fundamental chemistry of combustion. The overall objectives are to determine rate constants for elementary reactions and to elucidate the pathways of multichannel reactions. A multitechnique approach that features three independent experiments provides unique capabilities in performing reliable kinetic measurements over an exceptionally wide range in temperature, 300 to 2500 K. Recent kinetic work has focused on experimental studies and theoretical calculations of the methane dissociation system (CH{sub 4} + Ar {yields} CH{sub 3} + H + Ar and H + CH{sub 4} {yields} CH{sub 3} + H{sub 2}). Additionally, a discharge flow-photoionization mass spectrometer (DF-PIMS) experiment is used to determine branching fractions for multichannel reactions and to measure ionization thresholds of free radicals. Thus, these photoionization experiments generate data that are relevant to both reaction pathways studies (reaction dynamics) and fundamental thermochemical research. Two distinct advantages of performing PIMS with high intensity, tunable vacuum ultraviolet light at the National Synchrotron Light Source are high detection sensitivity and exceptional selectivity in monitoring radical species.

  12. Numerical Simulation of the Kinetic Critical Nucleus

    OpenAIRE

    Sanada, Masaaki; Nishioka, Kazumi; Okada, Masahumi; Maksimov, Igor, L.

    1997-01-01

    Our main interest is to see whether the number density indicates a peak at the kinetically stable critical nucleus due to its kinetical stability. We have numerically calculated the time evolution of the number densities of clusters in the case of water vapor nucleation. We employ the condition in which the difference between the size of the thermodynamic crtitical nucleus and that of the kinetic one is appreciable. The results show that the peak does not appear in the number densities of clu...

  13. Mixed La-Li heterobimetallic complexes for tertiary nitroaldol resolution.

    Science.gov (United States)

    Tosaki, Shin-ya; Hara, Keiichi; Gnanadesikan, Vijay; Morimoto, Hiroyuki; Harada, Shinji; Sugita, Mari; Yamagiwa, Noriyuki; Matsunaga, Shigeki; Shibasaki, Masakatsu

    2006-09-13

    A kinetic resolution of tertiary nitroaldols derived from simple ketones is described. Mixed BINOL/biphenol La-Li heterobimetallic complexes gave the best selectivity in retro-nitroaldol reactions of racemic tertiary nitroaldols. By using a mixture of La-Li3-(1a)3 complex (LLB 2a) and La-Li3-(1b)3 (LLB* 2b) complex in a ratio of 2/1, chiral tertiary nitroaldols were obtained in 80-97% ee and 30-47% recovery yield.

  14. Drug-Target Kinetics in Drug Discovery.

    Science.gov (United States)

    Tonge, Peter J

    2018-01-17

    The development of therapies for the treatment of neurological cancer faces a number of major challenges including the synthesis of small molecule agents that can penetrate the blood-brain barrier (BBB). Given the likelihood that in many cases drug exposure will be lower in the CNS than in systemic circulation, it follows that strategies should be employed that can sustain target engagement at low drug concentration. Time dependent target occupancy is a function of both the drug and target concentration as well as the thermodynamic and kinetic parameters that describe the binding reaction coordinate, and sustained target occupancy can be achieved through structural modifications that increase target (re)binding and/or that decrease the rate of drug dissociation. The discovery and deployment of compounds with optimized kinetic effects requires information on the structure-kinetic relationships that modulate the kinetics of binding, and the molecular factors that control the translation of drug-target kinetics to time-dependent drug activity in the disease state. This Review first introduces the potential benefits of drug-target kinetics, such as the ability to delineate both thermodynamic and kinetic selectivity, and then describes factors, such as target vulnerability, that impact the utility of kinetic selectivity. The Review concludes with a description of a mechanistic PK/PD model that integrates drug-target kinetics into predictions of drug activity.

  15. Tantalum high-temperature oxidation kinetics

    International Nuclear Information System (INIS)

    Grigor'ev, Yu.M.; Sarkisyan, A.A.; Merzhanov, A.G.

    1981-01-01

    Kinetics of heat release and scale growth during tantalum oxidation within 650-1300 deg C temperature range in oxygen-containing media is investigated. Kinetic equations and temperature and pressure dependences of constants are ound Applicability of the kinetic Lorie mechanism for the description of the tantalum oxidation kinetics applicably to rapid-passing processes is shown. It is stated that the process rate (reaction ability) is determined by adsorption desorption factors on the external surface of the ''protective'' oxide for the ''linear'' oxidation stage [ru

  16. Tele-AAC Resolution

    Directory of Open Access Journals (Sweden)

    Kate Anderson

    2012-12-01

    Full Text Available Approximately 1.3% of all people, or about 4 million Americans, cannot rely on their natural speech to meet their daily communication needs. Telepractice offers a potentially cost-effective service delivery mechanism to provide clinical AAC services at a distance to the benefit of underserved populations in the United States and worldwide.  Tele-AAC is a unique cross-disciplinary clinical service delivery model that requires expertise in both telepractice and augmentative and alternative communication (AAC systems.  The Tele-AAC Working Group of the 2012 ISAAC Research Symposium therefore drafted a resolution underscoring the importance of identifying and characterizing the unique opportunities and constraints of Tele-AAC in all aspects of service delivery. These include, but are not limited to: needs assessments; implementation planning; device/system procurement, set-up and training; quality assurance, client progress monitoring, and follow-up service delivery. Tele-AAC, like other telepractice applications, requires adherence to the ASHA Code of Ethics and other policy documents, and state, federal, and international laws, as well as a competent technological infrastructure. The Working Group recommends that institutions of higher education and professional organizations provide training in Tele-AAC service provision. In addition, research and development are needed to create validity measures across Tele-AAC practices (i.e., assessment, implementation, and consultation; determine the communication competence levels achieved  by Tele-AAC users; discern stakeholders’  perceptions of Tele-AAC services (e.g., acceptability and viability; maximize Tele-AAC’s capacity to engage multiple team members in AAC assessment and ongoing service; identify the limitations and barriers of Tele-AAC provision; and develop potential solutions. 

  17. Actinide immobilization in the subsurface environment by in-situ treatment with a hydrolytically unstable organophosphorus complexant: Uranyl uptake by calcium phytate

    International Nuclear Information System (INIS)

    Nash, K.L.; Jensen, M.P.; Schmidt, M.A.

    1997-01-01

    In addition to naturally occurring uranium and thorium, actinide ions exist in the subsurface environment as a result of accidental releases and intentional disposal practices associated with nuclear weapons production. These species present a significant challenge to cost-effective remediation of contaminated environments. An attractive approach to decreasing the probability of actinide migration in the subsurface is to transform the ions into a less mobile form by remote treatment. We have under development a process which relies on a polyfunctional organophosphorus complexant to sequester the mobile metal ions by complexation/cation exchange in the near term, and to subsequently decompose, transforming the actinides into insoluble phosphate mineral forms in the long term. Studies to date include identification of a suitable organophosphorus reagent, profiling of its decomposition kinetics, verification of the formation of phosphate mineral phases upon decomposition of the reagent, and extensive comparison of the actinide uptake ability of the calcium salt of the reagent as compared with hydroxyapatite. In this report, we briefly describe the process with focus on the cation exchange behavior of the calcium salt of the organophosphorus sequestrant

  18. Co-inoculating ruminal content neither provides active hydrolytic microbes nor improves methanization of ¹³C-cellulose in batch digesters.

    Science.gov (United States)

    Chapleur, Olivier; Bize, Ariane; Serain, Thibaut; Mazéas, Laurent; Bouchez, Théodore

    2014-03-01

    Cellulose hydrolysis often limits the kinetics and efficiency of anaerobic degradation in industrial digesters. In animal digestive systems, specialized microorganisms enable cellulose biodegradation at significantly higher rates. This study aims to assess the potential of ruminal microbial communities to settle and to express their cellulolytic properties in anaerobic digesters. Cellulose-degrading batch incubations were co-inoculated with municipal solid waste digester sludge and ruminal content. ¹³C-labeled cellulose degradation was described over time with Gas Chromatography-Combustion-Isotope Ratio Mass Spectrometry. Results were linked to the identification of the microorganisms assimilating ¹³C and to the monitoring of their relative dynamics. Cellulose degradation in co-inoculated incubations was efficient but not significantly improved. Transient disturbances in degradation pathways occurred, as revealed by propionate accumulation. Automated Ribosomal Intergenic Spacer Analysis dynamics and pyrosequencing revealed that expected classes of Bacteria and Archaea were active and degraded cellulose. However, despite the favorable co-inoculation conditions, molecular tools also revealed that no ruminal species settled in the bioreactors. Other specific parameters were probably needed for this to happen. This study shows that exploiting the rumen's cellulolytic properties in anaerobic digesters is not straightforward. Co-inoculation can only be successful if ruminal microorganisms manage to thrive in the anaerobic digester and outcompete native microorganisms, which requires specific nutritional and environmental parameters, and a meticulous reproduction of the selection pressure encountered in the rumen. © 2013 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

  19. Tailoring the degradation rate and release kinetics from poly(galactitol sebacate) by blending with chitosan, alginate or ethyl cellulose.

    Science.gov (United States)

    Natarajan, Janeni; Madras, Giridhar; Chatterjee, Kaushik

    2016-12-01

    Despite significant advances in recent times, the investigation of discovering a perfect biomaterial is perennial. In this backdrop, blending of natural and synthetic polymers is gaining popularity since it is the easiest way to complement the drawbacks and attain a superlative material. Based on this, the objective of this study was to synthesize a novel polyester, poly(galactitol sebacate), and subsequently blend this polymer with one of the three natural polymers such as alginate, chitosan or ethyl cellulose. FT-IR showed the presence of both the polymers in the blends. 1 H NMR confirmed the chemical structure of the synthesized poly (galactitol sebacate). Thermal characterization was performed by DSC revealing that the polymers were amorphous in nature and the glass transition temperatures increased with the increase in ratio of the natural polymers in the blends. SEM imaging showed that the blends were predominantly homogeneous. Contact angle measurements demonstrated that the blending imparted the hydrophilic nature into poly (galactitol sebacate) when blending with alginate or chitosan and hydrophobic when blending with ethyl cellulose. In vitro hydrolytic degradation studies and dye release studies indicated that the polymers became more hydrophilic in alginate and chitosan blends and thus accelerated the degradation and release process. The reverse trend was observed in the case of ethyl cellulose blends. Modeling elucidated that the degradation and dye release followed first order kinetics and Higuchi kinetics, respectively. In vitro cell studies confirmed the cytocompatible nature of the blends. It can be proposed that the chosen natural polymers for blending showed wide variations in hydrophilicity resulting in tailored degradation, release and cytocompatibility properties and thus are promising candidates for use in drug delivery and tissue engineering. Copyright © 2016 Elsevier B.V. All rights reserved.

  20. Surfactant disaturated-phosphatidylcholine kinetics in acute respiratory distress syndrome by stable isotopes and a two compartment model

    Directory of Open Access Journals (Sweden)

    Cogo Paola E

    2007-02-01

    Full Text Available Abstract Background In patients with acute respiratory distress syndrome (ARDS, it is well known that only part of the lungs is aerated and surfactant function is impaired, but the extent of lung damage and changes in surfactant turnover remain unclear. The objective of the study was to evaluate surfactant disaturated-phosphatidylcholine turnover in patients with ARDS using stable isotopes. Methods We studied 12 patients with ARDS and 7 subjects with normal lungs. After the tracheal instillation of a trace dose of 13C-dipalmitoyl-phosphatidylcholine, we measured the 13C enrichment over time of palmitate residues of disaturated-phosphatidylcholine isolated from tracheal aspirates. Data were interpreted using a model with two compartments, alveoli and lung tissue, and kinetic parameters were derived assuming that, in controls, alveolar macrophages may degrade between 5 and 50% of disaturated-phosphatidylcholine, the rest being lost from tissue. In ARDS we assumed that 5–100% of disaturated-phosphatidylcholine is degraded in the alveolar space, due to release of hydrolytic enzymes. Some of the kinetic parameters were uniquely determined, while others were identified as lower and upper bounds. Results In ARDS, the alveolar pool of disaturated-phosphatidylcholine was significantly lower than in controls (0.16 ± 0.04 vs. 1.31 ± 0.40 mg/kg, p de novo synthesis of disaturated-phosphatidylcholine were also significantly lower, while mean resident time in lung tissue was significantly higher in ARDS than in controls. Recycling was 16.2 ± 3.5 in ARDS and 31.9 ± 7.3 in controls (p = 0.08. Conclusion In ARDS the alveolar pool of surfactant is reduced and disaturated-phosphatidylcholine turnover is altered.

  1. Kinetics and mechanism of the biodegradation of PLA/clay nanocomposites during thermophilic phase of composting process.

    Science.gov (United States)

    Stloukal, Petr; Pekařová, Silvie; Kalendova, Alena; Mattausch, Hannelore; Laske, Stephan; Holzer, Clemens; Chitu, Livia; Bodner, Sabine; Maier, Guenther; Slouf, Miroslav; Koutny, Marek

    2015-08-01

    The degradation mechanism and kinetics of polylactic acid (PLA) nanocomposite films, containing various commercially available native or organo-modified montmorillonites (MMT) prepared by melt blending, were studied under composting conditions in thermophilic phase of process and during abiotic hydrolysis and compared to the pure polymer. Described first order kinetic models were applied on the data from individual experiments by using non-linear regression procedures to calculate parameters characterizing aerobic composting and abiotic hydrolysis, such as carbon mineralization, hydrolysis rate constants and the length of lag phase. The study showed that the addition of nanoclay enhanced the biodegradation of PLA nanocomposites under composting conditions, when compared with pure PLA, particularly by shortening the lag phase at the beginning of the process. Whereas the lag phase of pure PLA was observed within 27days, the onset of CO2 evolution for PLA with native MMT was detected after just 20days, and from 13 to 16days for PLA with organo-modified MMT. Similarly, the hydrolysis rate constants determined tended to be higher for PLA with organo-modified MMT, particularly for the sample PLA-10A with fastest degradation, in comparison with pure PLA. The acceleration of chain scission in PLA with nanoclays was confirmed by determining the resultant rate constants for the hydrolytical chain scission. The critical molecular weight for the hydrolysis of PLA was observed to be higher than the critical molecular weight for onset of PLA mineralization, suggesting that PLA chains must be further shortened so as to be assimilated by microorganisms. In conclusion, MMT fillers do not represent an obstacle to acceptance of the investigated materials in composting facilities. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Nonlinear saturation of the slab ITG instability and zonal flow generation with fully kinetic ions

    Science.gov (United States)

    Miecnikowski, Matthew T.; Sturdevant, Benjamin J.; Chen, Yang; Parker, Scott E.

    2018-05-01

    Fully kinetic turbulence models are of interest for their potential to validate or replace gyrokinetic models in plasma regimes where the gyrokinetic expansion parameters are marginal. Here, we demonstrate fully kinetic ion capability by simulating the growth and nonlinear saturation of the ion-temperature-gradient instability in shearless slab geometry assuming adiabatic electrons and including zonal flow dynamics. The ion trajectories are integrated using the Lorentz force, and the cyclotron motion is fully resolved. Linear growth and nonlinear saturation characteristics show excellent agreement with analogous gyrokinetic simulations across a wide range of parameters. The fully kinetic simulation accurately reproduces the nonlinearly generated zonal flow. This work demonstrates nonlinear capability, resolution of weak gradient drive, and zonal flow physics, which are critical aspects of modeling plasma turbulence with full ion dynamics.

  3. Super-resolution Phase Tomography

    KAUST Repository

    Depeursinge, Christian; Cotte, Yann; Toy, Fatih; Jourdain, Pascal; Boss, Daiel; Marquet, Pierre; Magistretti, Pierre J.

    2013-01-01

    Digital Holographic Microscopy (DHM) yields reconstructed complex wavefields. It allows synthesizing the aperture of a virtual microscope up to 2π, offering super-resolution phase images. Live images of micro-organisms and neurons with resolution less than 100 nm are presented.

  4. Resolution analysis by random probing

    NARCIS (Netherlands)

    Fichtner, Andreas; van Leeuwen, T.

    2015-01-01

    We develop and apply methods for resolution analysis in tomography, based on stochastic probing of the Hessian or resolution operators. Key properties of our methods are (i) low algorithmic complexity and easy implementation, (ii) applicability to any tomographic technique, including full‐waveform

  5. Super-resolution Phase Tomography

    KAUST Repository

    Depeursinge, Christian

    2013-04-21

    Digital Holographic Microscopy (DHM) yields reconstructed complex wavefields. It allows synthesizing the aperture of a virtual microscope up to 2π, offering super-resolution phase images. Live images of micro-organisms and neurons with resolution less than 100 nm are presented.

  6. "Planar" Tautologies Hard for Resolution

    DEFF Research Database (Denmark)

    Dantchev, Stefan; Riis, Søren

    2001-01-01

    We prove exponential lower bounds on the resolution proofs of some tautologies, based on rectangular grid graphs. More specifically, we show a 2Ω(n) lower bound for any resolution proof of the mutilated chessboard problem on a 2n×2n chessboard as well as for the Tseitin tautology (G. Tseitin, 196...

  7. Resolution function in neutron diffractometry

    International Nuclear Information System (INIS)

    Popa, N.

    1987-01-01

    The resolution function in the neutron diffractometry is defined, on base of generalizing the resolution formerly formulated for the double axis neutron spectrometer. A polemical discussion is raised concerning an approach to this function existent in literature. The actual approach is concretized for the DN-2 time-of-flight diffractometer installed at the IBR-2 reactor

  8. Breaking time-resolution limits in pulse radiolysis

    International Nuclear Information System (INIS)

    Yang Jinfeng; Kondoh, Takafumi; Norizawa, Kimihiro; Yoshida, Yoichi; Tagawa, Seiichi

    2009-01-01

    Pulse radiolysis, which is a time-resolved stroboscopic method based on ultrashort electron pulse and ultrashort analyzing light, is widely used for the study of the chemical kinetics and radiation primary processes or reactions. Although it has become possible to use femtosecond-pulse electron beam and femtosecond laser light in pulse radiolysis, the resolution is limited by the difference in group velocities of the electrons and the light in sample. In this contribution, we introduce a concept of equivalent velocity spectroscopy (EVS) into pulse radiolysis and demonstrate the methodology experimentally. In EVS, both the electron and the analyzing light pulses precisely overlap at every point in the sample and throughout the propagation time by rotating the electron pulse. The advance allows us to overcome the resolution degradation due to the different group velocity. We also present a method for measuring the rotated angle of the electron pulse and a technique for rotating the electron pulse with a deflecting cavity.

  9. Electron microscopy at atomic resolution

    Energy Technology Data Exchange (ETDEWEB)

    Gronsky, R.

    1983-11-01

    The direct imaging of atomic structure in solids has become increasingly easier to accomplish with modern transmission electron microscopes, many of which have an information retrieval limit near 0.2 nm point resolution. Achieving better resolution, particularly with any useful range of specimen tilting, requires a major design effort. This presentation describes the new Atomic Resolution Microscope (ARM), recently put into operation at the Lawrence Berkeley Laboratory. Capable of 0.18 nm or better interpretable resolution over a voltage range of 400 kV to 1000 kV with +- 40/sup 0/ biaxial specimen tilting, the ARM features a number of new electron-optical and microprocessor-control designs. These are highlighted, and its atomic resolution performance demonstrated for a selection of inorganic crystals.

  10. Electron microscopy at atomic resolution

    International Nuclear Information System (INIS)

    Gronsky, R.

    1983-11-01

    The direct imaging of atomic structure in solids has become increasingly easier to accomplish with modern transmission electron microscopes, many of which have an information retrieval limit near 0.2 nm point resolution. Achieving better resolution, particularly with any useful range of specimen tilting, requires a major design effort. This presentation describes the new Atomic Resolution Microscope (ARM), recently put into operation at the Lawrence Berkeley Laboratory. Capable of 0.18 nm or better interpretable resolution over a voltage range of 400 kV to 1000 kV with +- 40 0 biaxial specimen tilting, the ARM features a number of new electron-optical and microprocessor-control designs. These are highlighted, and its atomic resolution performance demonstrated for a selection of inorganic crystals

  11. Disordering kinetics in surface overlayers

    International Nuclear Information System (INIS)

    Jesina, A.; Tringides, M.C.

    1993-01-01

    The disordering kinetics of the O/W(110)-p(2x1)+p(2x2) overlayer, prepared initially in a well-ordered state, are studied with low-energy electron diffraction profile analysis. The decay of the peak intensity, used as a measure of the growing disorder, cannot be fitted to a power law as in the case of ordering processes. The full width at half maximum of the time-dependent structure factor S(q,t) is constant with time, which suggests that the average size remains constant. Diffusion activation energy extracted for the temperature dependence of the disordering is 1.0±0.05 eV, which is different from the value of 0.6 eV measured in ordering processes. The difference can be explained by the adsorbate-adsorbate interactions, which contribute differently to the diffusion barrier, in the two experiments

  12. Analysis of kinetic reaction mechanisms

    CERN Document Server

    Turányi, Tamás

    2014-01-01

    Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods for the analysis of reaction mechanisms that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.

  13. Nuclear reactor kinetics and control

    International Nuclear Information System (INIS)

    Lewins, J.

    1978-01-01

    A consistent, integrated account of modern developments in the study of nuclear reactor kinetics and the problem of their efficient and safe control. It aims to prepare the student for advanced study and research or practical work in the field. Special features include treatments of noise theory, reliability theory and safety related studies. It covers all aspects of the operation and control of nuclear reactors, power and research and is complete in providing physical data methods of calculation and solution including questions of equipment reliability. The work uses illustrations of the main types of reactors in use in the UK, USA and Europe. Each chapter contains problems and worked examples suitable for course work and study. The subject is covered in chapters, entitled: introductory review; neutron and precursor equations; elementary solutions at low power; linear reactor process dynamics with feedback; power reactor control systems; fluctuations and reactor noise; safety and reliability; nonlinear systems (safety and control); analogue computing. (author)

  14. Method of molybdenum kinetic determination

    International Nuclear Information System (INIS)

    Krejngol'd, S.U.; Dzotsenidze, N.E.; Ruseishviyai, T.G.; Nelen', I.M.

    1980-01-01

    The method molybdenum kinetic determination according to oxidation of pyrogallol with bromate in the medium of 0.05-0.15 M perchloric or sulphuric acids is presented. 1 mg of Ni, Co, Mn, Mg, Zn, Cr(3); 100 μg of Ca, Al, Cu, 10 μg of Cr(4), W; 10 μg of Fe in the presence of 22x10 - 4 M solution of EDTA, as well as 10 - 4 M solutions of chlorides and fluorides, 10 - 5 M solutions of bromides do not interfere with molybdenum determination using the given method. The method is rather simple, it takes 30 min to carry out the analysis. Determination limit of molybdenum constitutes 0.01 μg/ml

  15. Quantum-statistical kinetic equations

    International Nuclear Information System (INIS)

    Loss, D.; Schoeller, H.

    1989-01-01

    Considering a homogeneous normal quantum fluid consisting of identical interacting fermions or bosons, the authors derive an exact quantum-statistical generalized kinetic equation with a collision operator given as explicit cluster series where exchange effects are included through renormalized Liouville operators. This new result is obtained by applying a recently developed superoperator formalism (Liouville operators, cluster expansions, symmetrized projectors, P q -rule, etc.) to nonequilibrium systems described by a density operator ρ(t) which obeys the von Neumann equation. By means of this formalism a factorization theorem is proven (being essential for obtaining closed equations), and partial resummations (leading to renormalized quantities) are performed. As an illustrative application, the quantum-statistical versions (including exchange effects due to Fermi-Dirac or Bose-Einstein statistics) of the homogeneous Boltzmann (binary collisions) and Choh-Uhlenbeck (triple collisions) equations are derived

  16. Growth kinetics in multicomponent fluids

    International Nuclear Information System (INIS)

    Chen, S.; Lookman, T.

    1995-01-01

    The hydrodynamic effects on the late-stage kinetics in spinodal decomposition of multicomponent fluids are examined using a lattice Boltzmann scheme with stochastic fluctuations in the fluid and at the interface. In two dimensions, the three- and four-component immiscible fluid mixture (with a 1024 2 lattice) behaves like an off-critical binary fluid with an estimated domain growth of t 0.4 +/= 0.03 rather than t 1/3 as previously estimated, showing the significant influence of hydrodynamics. In three dimensions (with a 256 3 lattice), we estimate the growth as t 0.96 +/= 0.05 for both critical and off-critical quenches, in agreement with phenomenological theory

  17. NESTLE: A nodal kinetics code

    International Nuclear Information System (INIS)

    Al-Chalabi, R.M.; Turinsky, P.J.; Faure, F.-X.; Sarsour, H.N.; Engrand, P.R.

    1993-01-01

    The NESTLE nodal kinetics code has been developed for utilization as a stand-alone code for steady-state and transient reactor neutronic analysis and for incorporation into system transient codes, such as TRAC and RELAP. The latter is desirable to increase the simulation fidelity over that obtained from currently employed zero- and one-dimensional neutronic models and now feasible due to advances in computer performance and efficiency of nodal methods. As a stand-alone code, requirements are that it operate on a range of computing platforms from memory-limited personal computers (PCs) to supercomputers with vector processors. This paper summarizes the features of NESTLE that reflect the utilization and requirements just noted

  18. Highly multiplexible thermal kinetic inductance detectors for x-ray imaging spectroscopy

    International Nuclear Information System (INIS)

    Ulbricht, Gerhard; Mazin, Benjamin A.; Szypryt, Paul; Walter, Alex B.; Bockstiegel, Clint; Bumble, Bruce

    2015-01-01

    For X-ray imaging spectroscopy, high spatial resolution over a large field of view is often as important as high energy resolution, but current X-ray detectors do not provide both in the same device. Thermal Kinetic Inductance Detectors (TKIDs) are being developed as they offer a feasible way to combine the energy resolution of transition edge sensors with pixel counts approaching CCDs and thus promise significant improvements for many X-ray spectroscopy applications. TKIDs are a variation of Microwave Kinetic Inductance Detectors (MKIDs) and share their multiplexibility: working MKID arrays with 2024 pixels have recently been demonstrated and much bigger arrays are under development. In this work, we present a TKID prototype, which is able to achieve an energy resolution of 75 eV at 5.9 keV, even though its general design still has to be optimized. We further describe TKID fabrication, characterization, multiplexing, and working principle and demonstrate the necessity of a data fitting algorithm in order to extract photon energies. With further design optimizations, we expect to be able to improve our TKID energy resolution to less than 10 eV at 5.9 keV

  19. Highly multiplexible thermal kinetic inductance detectors for x-ray imaging spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ulbricht, Gerhard, E-mail: ulbricht@physics.ucsb.edu; Mazin, Benjamin A.; Szypryt, Paul; Walter, Alex B.; Bockstiegel, Clint [Department of Physics, University of California, Santa Barbara, California 93106 (United States); Bumble, Bruce [NASA Jet Propulsion Laboratory, 4800 Oak Grove Drive, Pasadena, California 91125 (United States)

    2015-06-22

    For X-ray imaging spectroscopy, high spatial resolution over a large field of view is often as important as high energy resolution, but current X-ray detectors do not provide both in the same device. Thermal Kinetic Inductance Detectors (TKIDs) are being developed as they offer a feasible way to combine the energy resolution of transition edge sensors with pixel counts approaching CCDs and thus promise significant improvements for many X-ray spectroscopy applications. TKIDs are a variation of Microwave Kinetic Inductance Detectors (MKIDs) and share their multiplexibility: working MKID arrays with 2024 pixels have recently been demonstrated and much bigger arrays are under development. In this work, we present a TKID prototype, which is able to achieve an energy resolution of 75 eV at 5.9 keV, even though its general design still has to be optimized. We further describe TKID fabrication, characterization, multiplexing, and working principle and demonstrate the necessity of a data fitting algorithm in order to extract photon energies. With further design optimizations, we expect to be able to improve our TKID energy resolution to less than 10 eV at 5.9 keV.

  20. Highest Resolution Gaspra Mosaic

    Science.gov (United States)

    1992-01-01

    This picture of asteroid 951 Gaspra is a mosaic of two images taken by the Galileo spacecraft from a range of 5,300 kilometers (3,300 miles), some 10 minutes before closest approach on October 29, 1991. The Sun is shining from the right; phase angle is 50 degrees. The resolution, about 54 meters/pixel, is the highest for the Gaspra encounter and is about three times better than that in the view released in November 1991. Additional images of Gaspra remain stored on Galileo's tape recorder, awaiting playback in November. Gaspra is an irregular body with dimensions about 19 x 12 x 11 kilometers (12 x 7.5 x 7 miles). The portion illuminated in this view is about 18 kilometers (11 miles) from lower left to upper right. The north pole is located at upper left; Gaspra rotates counterclockwise every 7 hours. The large concavity on the lower right limb is about 6 kilometers (3.7 miles) across, the prominent crater on the terminator, center left, about 1.5 kilometers (1 mile). A striking feature of Gaspra's surface is the abundance of small craters. More than 600 craters, 100-500 meters (330-1650 feet) in diameter are visible here. The number of such small craters compared to larger ones is much greater for Gaspra than for previously studied bodies of comparable size such as the satellites of Mars. Gaspra's very irregular shape suggests that the asteroid was derived from a larger body by nearly catastrophic collisions. Consistent with such a history is the prominence of groove-like linear features, believed to be related to fractures. These linear depressions, 100-300 meters wide and tens of meters deep, are in two crossing groups with slightly different morphology, one group wider and more pitted than the other. Grooves had previously been seen only on Mars's moon Phobos, but were predicted for asteroids as well. Gaspra also shows a variety of enigmatic curved depressions and ridges in the terminator region at left. The Galileo project, whose primary mission is the

  1. Gaspra - Highest Resolution Mosaic

    Science.gov (United States)

    1992-01-01

    This picture of asteroid 951 Gaspra is a mosaic of two images taken by the Galileo spacecraft from a range of 5,300 kilometers (3,300 miles), some 10 minutes before closest approach on October 29, 1991. The Sun is shining from the right; phase angle is 50 degrees. The resolution, about 54 meters/pixel, is the highest for the Gaspra encounter and is about three times better than that in the view released in November 1991. Additional images of Gaspra remain stored on Galileo's tape recorder, awaiting playback in November. Gaspra is an irregular body with dimensions about 19 x 12 x 11 kilometers (12 x 7.5 x 7 miles). The portion illuminated in this view is about 18 kilometers (11 miles) from lower left to upper right. The north pole is located at upper left; Gaspra rotates counterclockwise every 7 hours. The large concavity on the lower right limb is about 6 kilometers (3.7 miles) across, the prominent crater on the terminator, center left, about 1.5 kilometers (1 mile). A striking feature of Gaspra's surface is the abundance of small craters. More than 600 craters, 100-500 meters (330-1650 feet) in diameter are visible here. The number of such small craters compared to larger ones is much greater for Gaspra than for previously studied bodies of comparable size such as the satellites of Mars. Gaspra's very irregular shape suggests that the asteroid was derived from a larger body by nearly catastrophic collisions. Consistent with such a history is the prominence of groove-like linear features, believed to be related to fractures. These linear depressions, 100-300 meters wide and tens of meters deep, are in two crossing groups with slightly different morphology, one group wider and more pitted than the other. Grooves had previously been seen only on Mars's moon Phobos, but were predicted for asteroids as well. Gaspra also shows a variety of enigmatic curved depressions and ridges in the terminator region at left. The Galileo project, whose primary mission is the

  2. Kinetics model for lutate dosimetry

    International Nuclear Information System (INIS)

    Lima, M.F.; Mesquita, C.H.

    2013-01-01

    The use of compartmental analysis to predict the behavior of drugs in the organism is considered the better option among numerous methods employed in pharmacodynamics. A six compartments model was developed to determinate the kinetic constants of 177Lu-DOTATATO biodistribution using data from one published study with 67 patients treated by PRRT (Peptide receptor radionuclide therapy) and followed by CT during 68,25 hours. The compartmental analysis was made using the software AnaComp®. The influence of the time pos-injection over the dose assessment was studied taking into account the renal excretion management by aminoacid coinfusion, whose direct effects persist in the first day. The biodistribution curve was split in five sectors: 0-0.25h; 0-3.25h; 3.25-24.25h; 24.25-68.25h and 3.25-68.25h. After the examination of that influence, the study was concentrated in separate the biodistribution curve in two phases. Phase 1: governed by uptake from the blood, considering the time pos-injection until 3.25h and phase 2: governed by renal excretion, considering the time pos-injection from 3.25h to 68.25h. The model considered the organs and tissues superposition in the CT image acquisition by sampling parameters as the contribution of the the activity concentration in blood and relation between the sizes of the whole body and measured organs. The kinetic constants obtained from each phase (1 and 2) were used in dose assessment to patients in 26 organs and tissues described by MIRD. Dosimetry results were in agreement with the available results from literature, restrict to whole body, kidneys, bone marrow, spleen and liver. The advantage of the proposed model is the compartmental method quickness and power to estimate dose in organs and tissues, including tumor that, in the most part, were not discriminate by voxels of phantoms built using CT images. (author)

  3. Nanoparticle shape, thermodynamics and kinetics

    International Nuclear Information System (INIS)

    Marks, L D; Peng, L

    2016-01-01

    Nanoparticles can be beautiful, as in stained glass windows, or they can be ugly as in wear and corrosion debris from implants. We estimate that there will be about 70 000 papers in 2015 with nanoparticles as a keyword, but only one in thirteen uses the nanoparticle shape as an additional keyword and research focus, and only one in two hundred has thermodynamics. Methods for synthesizing nanoparticles have exploded over the last decade, but our understanding of how and why they take their forms has not progressed as fast. This topical review attempts to take a critical snapshot of the current understanding, focusing more on methods to predict than a purely synthetic or descriptive approach. We look at models and themes which are largely independent of the exact synthetic method whether it is deposition, gas-phase condensation, solution based or hydrothermal synthesis. Elements are old dating back to the beginning of the 20th century—some of the pioneering models developed then are still relevant today. Others are newer, a merging of older concepts such as kinetic-Wulff constructions with methods to understand minimum energy shapes for particles with twins. Overall we find that while there are still many unknowns, the broad framework of understanding and predicting the structure of nanoparticles via diverse Wulff constructions, either thermodynamic, local minima or kinetic has been exceedingly successful. However, the field is still developing and there remain many unknowns and new avenues for research, a few of these being suggested towards the end of the review. (topical review)

  4. Kinetics model for lutate dosimetry

    Energy Technology Data Exchange (ETDEWEB)

    Lima, M.F.; Mesquita, C.H., E-mail: mflima@ipen.br, E-mail: chmesqui@ipen.br [Instituto de Pesquisas Energeticas (IPEN/CNEN-SP), Sao Paulo, SP (Brazil)

    2013-11-01

    The use of compartmental analysis to predict the behavior of drugs in the organism is considered the better option among numerous methods employed in pharmacodynamics. A six compartments model was developed to determinate the kinetic constants of 177Lu-DOTATATO biodistribution using data from one published study with 67 patients treated by PRRT (Peptide receptor radionuclide therapy) and followed by CT during 68,25 hours. The compartmental analysis was made using the software AnaComp Registered-Sign . The influence of the time pos-injection over the dose assessment was studied taking into account the renal excretion management by aminoacid coinfusion, whose direct effects persist in the first day. The biodistribution curve was split in five sectors: 0-0.25h; 0-3.25h; 3.25-24.25h; 24.25-68.25h and 3.25-68.25h. After the examination of that influence, the study was concentrated in separate the biodistribution curve in two phases. Phase 1: governed by uptake from the blood, considering the time pos-injection until 3.25h and phase 2: governed by renal excretion, considering the time pos-injection from 3.25h to 68.25h. The model considered the organs and tissues superposition in the CT image acquisition by sampling parameters as the contribution of the the activity concentration in blood and relation between the sizes of the whole body and measured organs. The kinetic constants obtained from each phase (1 and 2) were used in dose assessment to patients in 26 organs and tissues described by MIRD. Dosimetry results were in agreement with the available results from literature, restrict to whole body, kidneys, bone marrow, spleen and liver. The advantage of the proposed model is the compartmental method quickness and power to estimate dose in organs and tissues, including tumor that, in the most part, were not discriminate by voxels of phantoms built using CT images. (author)

  5. Resolution enhancement techniques in microscopy

    Science.gov (United States)

    Cremer, Christoph; Masters, Barry R.

    2013-05-01

    We survey the history of resolution enhancement techniques in microscopy and their impact on current research in biomedicine. Often these techniques are labeled superresolution, or enhanced resolution microscopy, or light-optical nanoscopy. First, we introduce the development of diffraction theory in its relation to enhanced resolution; then we explore the foundations of resolution as expounded by the astronomers and the physicists and describe the conditions for which they apply. Then we elucidate Ernst Abbe's theory of optical formation in the microscope, and its experimental verification and dissemination to the world wide microscope communities. Second, we describe and compare the early techniques that can enhance the resolution of the microscope. Third, we present the historical development of various techniques that substantially enhance the optical resolution of the light microscope. These enhanced resolution techniques in their modern form constitute an active area of research with seminal applications in biology and medicine. Our historical survey of the field of resolution enhancement uncovers many examples of reinvention, rediscovery, and independent invention and development of similar proposals, concepts, techniques, and instruments. Attribution of credit is therefore confounded by the fact that for understandable reasons authors stress the achievements from their own research groups and sometimes obfuscate their contributions and the prior art of others. In some cases, attribution of credit is also made more complex by the fact that long term developments are difficult to allocate to a specific individual because of the many mutual connections often existing between sometimes fiercely competing, sometimes strongly collaborating groups. Since applications in biology and medicine have been a major driving force in the development of resolution enhancing approaches, we focus on the contribution of enhanced resolution to these fields.

  6. Hydrodynamic chronoamperometry for probing kinetics of anaerobic microbial metabolism--case study of Faecalibacterium prausnitzii.

    Science.gov (United States)

    Prévoteau, Antonin; Geirnaert, Annelies; Arends, Jan B A; Lannebère, Sylvain; Van de Wiele, Tom; Rabaey, Korneel

    2015-07-01

    Monitoring in vitro the metabolic activity of microorganisms aids bioprocesses and enables better understanding of microbial metabolism. Redox mediators can be used for this purpose via different electrochemical techniques that are either complex or only provide non-continuous data. Hydrodynamic chronoamperometry using a rotating disc electrode (RDE) can alleviate these issues but was seldom used and is poorly characterized. The kinetics of Faecalibacterium prausnitzii A2-165, a beneficial gut microbe, were determined using a RDE with riboflavin as redox probe. This butyrate producer anaerobically ferments glucose and reduces riboflavin whose continuous monitoring on a RDE provided highly accurate kinetic measurements of its metabolism, even at low cell densities. The metabolic reaction rate increased linearly over a broad range of cell concentrations (9 × 10(4) to 5 × 10(7) cells.mL(-1)). Apparent Michaelis-Menten kinetics was observed with respect to riboflavin (KM = 6 μM; kcat = 5.3 × 10(5) s(-1), at 37 °C) and glucose (KM = 6 μM; kcat = 2.4 × 10(5) s(-1)). The short temporal resolution allows continuous monitoring of fast cellular events such as kinetics inhibition with butyrate. Furthermore, we detected for the first time riboflavin reduction by another potential probiotic, Butyricicoccus pullicaecorum. The ability of the RDE for fast, accurate, simple and continuous measurements makes it an ad hoc tool for assessing bioprocesses at high resolution.

  7. Femto-clock for the electron kinetics in swift heavy ion tracks

    Czech Academy of Sciences Publication Activity Database

    Medvedev, Nikita; Volkov, A.E.

    2017-01-01

    Roč. 50, č. 44 (2017), s. 1-11, č. článku 445302. ISSN 0022-3727 R&D Projects: GA MŠk LG15013; GA MŠk(CZ) LM2015083 Institutional support: RVO:68378271 Keywords : swift heavy ions * electron kinetics * femto-clock * femtosecond resolution * spectroscopy * radiative decay Subject RIV: BL - Plasma and Gas Discharge Physics OBOR OECD: Fluids and plasma physics (including surface physics) Impact factor: 2.588, year: 2016

  8. Conformational Diffusion and Helix Formation Kinetics

    International Nuclear Information System (INIS)

    Hummer, Gerhard; Garcia, Angel E.; Garde, Shekhar

    2000-01-01

    The time, temperature, and sequence dependences of helix formation kinetics of fully atomistic peptide models in explicit solvent are described quantitatively by a diffusive search within the coil state with barrierless transitions into the helical state. Conformational diffusion leads to nonexponential kinetics and jump-width dependences in temperature jump experiments. (c) 2000 The American Physical Society

  9. Towards Free-Form Kinetic Structures

    DEFF Research Database (Denmark)

    Parigi, Dario; Kirkegaard, Poul Henning

    2012-01-01

    of pin-slot paths starting from the local displacements of element [2] [3]. In the design of kinetic structures, in particular when complex three dimensional and non regular configurations are involved, the functionality is frequently related to a global displacement capability of the assembly rather...... for the generation of free-form kinetic structures....

  10. Modeling composting kinetics: A review of approaches

    NARCIS (Netherlands)

    Hamelers, H.V.M.

    2004-01-01

    Composting kinetics modeling is necessary to design and operate composting facilities that comply with strict market demands and tight environmental legislation. Current composting kinetics modeling can be characterized as inductive, i.e. the data are the starting point of the modeling process and

  11. Saffman-Taylor fingers with kinetic undercooling

    KAUST Repository

    Gardiner, Bennett P. J.

    2015-02-23

    © 2015 American Physical Society. The mathematical model of a steadily propagating Saffman-Taylor finger in a Hele-Shaw channel has applications to two-dimensional interacting streamer discharges which are aligned in a periodic array. In the streamer context, the relevant regularization on the interface is not provided by surface tension but instead has been postulated to involve a mechanism equivalent to kinetic undercooling, which acts to penalize high velocities and prevent blow-up of the unregularized solution. Previous asymptotic results for the Hele-Shaw finger problem with kinetic undercooling suggest that for a given value of the kinetic undercooling parameter, there is a discrete set of possible finger shapes, each analytic at the nose and occupying a different fraction of the channel width. In the limit in which the kinetic undercooling parameter vanishes, the fraction for each family approaches 1/2, suggesting that this "selection" of 1/2 by kinetic undercooling is qualitatively similar to the well-known analog with surface tension. We treat the numerical problem of computing these Saffman-Taylor fingers with kinetic undercooling, which turns out to be more subtle than the analog with surface tension, since kinetic undercooling permits finger shapes which are corner-free but not analytic. We provide numerical evidence for the selection mechanism by setting up a problem with both kinetic undercooling and surface tension and numerically taking the limit that the surface tension vanishes.

  12. Chemical kinetics and oil shale process design

    Energy Technology Data Exchange (ETDEWEB)

    Burnham, A.K.

    1993-07-01

    Oil shale processes are reviewed with the goal of showing how chemical kinetics influences the design and operation of different processes for different types of oil shale. Reaction kinetics are presented for organic pyrolysis, carbon combustion, carbonate decomposition, and sulfur and nitrogen reactions.

  13. A Comprehensive Enzyme Kinetic Exercise for Biochemistry

    Science.gov (United States)

    Barton, Janice S.

    2011-01-01

    This article describes a comprehensive treatment of experimental enzyme kinetics strongly coupled to electronic data acquisition and use of spreadsheets to organize data and perform linear and nonlinear least-squares analyses, all in a manner that promotes development of important reasoning skills. Kinetic parameters are obtained for the stable…

  14. Kinetic equations for the collisional plasma model

    International Nuclear Information System (INIS)

    Rij, W.I. Van; Meier, H.K.; Beasley, C.O. Jr.; McCune, J.E.

    1977-01-01

    Using the Collisional Plasma Model (CPM) representation, expressions are derived for the Vlasov operator, both in its general form and in the drift-kinetic approximation following the recursive derivation by Hazeltine. The expressions for the operators give easily calculated couplings between neighbouring components of the CPM representation. Expressions for various macroscopic observables in the drift-kinetics approximation are also given. (author)

  15. Chemistry and reaction kinetics of biowaste torrefaction

    NARCIS (Netherlands)

    Stelt, van der M.J.C.

    2011-01-01

    This thesis addresses the question of how the chemistry and reaction kinetics of torrefaction are influenced by reaction conditions and the effects occuring during the reaction. This research question can be specified by questions such as, what controls their kinetics during torrefaction and what

  16. Determination of the kinetics of ethene epoxidation

    NARCIS (Netherlands)

    Schouten, E.P.S.; Schouten, E.P.S.; Borman, P.C.; Borman, P.C.; Westerterp, K.R.

    1996-01-01

    Several problems and pitfalls in the use of laboratory reactors for the determination of the kinetics of ethene epoxidation over industrial silver on α-alumina catalyst are discussed. Also, commonly used methodologies for kinetic studies are dealt with because of the general nature of some problems.

  17. Kinetic spectrophotometric determination of some fluoroquinolone ...

    African Journals Online (AJOL)

    A simple and sensitive kinetic spectrophotometric method was developed for the determination of some fluoroquinolonea antibiotics; gemifloxacin mesylate, moxifloxacin hydrochloride and gatifloxacin in bulk and in pharmaceutical preparations. The method is based upon a kinetic investigation of the oxidation reaction of ...

  18. Saffman-Taylor fingers with kinetic undercooling

    KAUST Repository

    Gardiner, Bennett P. J.; McCue, Scott W.; Dallaston, Michael C.; Moroney, Timothy J.

    2015-01-01

    © 2015 American Physical Society. The mathematical model of a steadily propagating Saffman-Taylor finger in a Hele-Shaw channel has applications to two-dimensional interacting streamer discharges which are aligned in a periodic array. In the streamer context, the relevant regularization on the interface is not provided by surface tension but instead has been postulated to involve a mechanism equivalent to kinetic undercooling, which acts to penalize high velocities and prevent blow-up of the unregularized solution. Previous asymptotic results for the Hele-Shaw finger problem with kinetic undercooling suggest that for a given value of the kinetic undercooling parameter, there is a discrete set of possible finger shapes, each analytic at the nose and occupying a different fraction of the channel width. In the limit in which the kinetic undercooling parameter vanishes, the fraction for each family approaches 1/2, suggesting that this "selection" of 1/2 by kinetic undercooling is qualitatively similar to the well-known analog with surface tension. We treat the numerical problem of computing these Saffman-Taylor fingers with kinetic undercooling, which turns out to be more subtle than the analog with surface tension, since kinetic undercooling permits finger shapes which are corner-free but not analytic. We provide numerical evidence for the selection mechanism by setting up a problem with both kinetic undercooling and surface tension and numerically taking the limit that the surface tension vanishes.

  19. Concepts of radial and angular kinetic energies

    DEFF Research Database (Denmark)

    Dahl, Jens Peder; Schleich, W.P.

    2002-01-01

    We consider a general central-field system in D dimensions and show that the division of the kinetic energy into radial and angular parts proceeds differently in the wave-function picture and the Weyl-Wigner phase-space picture, Thus, the radial and angular kinetic energies are different quantities...

  20. Conformational Diffusion and Helix Formation Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Hummer, Gerhard [Laboratory of Chemical Physics, Building 5, National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, Maryland 20892-0520 (United States); Garcia, Angel E. [Theoretical Biology and Biophysics Group T-10, MS K710, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States); Garde, Shekhar [Department of Chemical Engineering, Rensselaer Polytechnic Institute, 110 8th Street, Troy, New York 12180 (United States)

    2000-09-18

    The time, temperature, and sequence dependences of helix formation kinetics of fully atomistic peptide models in explicit solvent are described quantitatively by a diffusive search within the coil state with barrierless transitions into the helical state. Conformational diffusion leads to nonexponential kinetics and jump-width dependences in temperature jump experiments. (c) 2000 The American Physical Society.

  1. Inflation Rates, Car Devaluation, and Chemical Kinetics.

    Science.gov (United States)

    Pogliani, Lionello; Berberan-Santos, Mario N.

    1996-01-01

    Describes the inflation rate problem and offers an interesting analogy with chemical kinetics. Presents and solves the car devaluation problem as a normal chemical kinetic problem where the order of the rate law and the value of the rate constant are derived. (JRH)

  2. Kinetic theory of gases and plasmas

    International Nuclear Information System (INIS)

    Schram, P.P.J.M.

    1991-01-01

    Kinetic theory provides the link between the non-equilibrium statistical mechanics of many-particle systems and macroscopic or phenomenological physics. This volume deals with the derivation of kinetic equations, their limitations and generalizations,and with the applications of kinetic theory to physical phenomena and the calculation of transport coefficients. This book is divided in 12 chapters which discuss a wide range of topics such as balanced equations, the Klimontovich, Vlasov-Maxwell, and Boltzmann equations, Chapman-Enskog theory, the kinetic theory of plasmas, B.G.K. models, linear response theory, Brownian motion and renormalized kinetic theory. Each chapter is concluded with exercises, which not only enable the readers to test their understanding of the theory, but also present additional examples which complement the text. 151 refs.; 35 figs.; 5 tabs

  3. Crystallization Kinetics within a Generic Modeling Framework

    DEFF Research Database (Denmark)

    Meisler, Kresten Troelstrup; von Solms, Nicolas; Gernaey, Krist V.

    2014-01-01

    of employing a well-structured model library for storage, use/reuse, and analysis of the kinetic models are highlighted. Examples illustrating the application of the modeling framework for kinetic model discrimination related to simulation of specific crystallization scenarios and for kinetic model parameter......A new and extended version of a generic modeling framework for analysis and design of crystallization operations is presented. The new features of this framework are described, with focus on development, implementation, identification, and analysis of crystallization kinetic models. Issues related...... to the modeling of various kinetic phenomena like nucleation, growth, agglomeration, and breakage are discussed in terms of model forms, model parameters, their availability and/or estimation, and their selection and application for specific crystallization operational scenarios under study. The advantages...

  4. Hydrogen electrode reaction: A complete kinetic description

    International Nuclear Information System (INIS)

    Quaino, P.M.; Gennero de Chialvo, M.R.; Chialvo, A.C.

    2007-01-01

    The kinetic description of the hydrogen electrode reaction (HER) in the whole range of overpotentials (-0.2 < η (V) < 0.40) is presented. The Volmer-Heyrovsky-Tafel mechanism was solved considering simultaneously the following items: (i) the diffusional contribution of the molecular hydrogen from and towards the electrode surface, (ii) the forward and backward reaction rates of each elementary step and (iii) a Frumkin type adsorption for the reaction intermediate. In order to verify the descriptive capability of the kinetic expressions derived, an experimental study of the HER was carried out on a rotating platinum disc electrode in acid solution. From the correlation of these results the elementary kinetic parameters were evaluated and several aspects related to the kinetic mechanism were discussed. Finally, the use of these kinetic expressions to interpret results obtained on microelectrodes is also analysed

  5. Kinetic advantage of controlled intermediate nuclear fusion

    International Nuclear Information System (INIS)

    Guo Xiaoming

    2012-01-01

    The dominated process of controlled fusion is to let nuclei gain enough kinetic energy to overcome Coulomb barrier. As a result, a fusion scheme can consider two factors in its design: to increase kinetic energy of nuclei and to alter the Coulomb barrier. Cold Fusion and Hot fusion are all one-factor schemes while Intermediate Fusion is a twofactors scheme. This made CINF kinetically superior. Cold Fusion reduces deuteron-deuteron distance, addressing Coulomb barrier, and Hot Fusion heat up plasma into extreme high temperature, addressing kinetic energy. Without enough kinetic energy made Cold Fusion skeptical. Extreme high temperature made Hot Fusion very difficult to engineer. Because CIFN addresses both factors, CIFN is a more promising technique to be industrialized.

  6. Dual enzymatic dynamic kinetic resolution by Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase and Candida antarctica lipase B

    KAUST Repository

    Karume, Ibrahim; Musa, Musa M.; Bsharat, Odey; Takahashi, Masateru; Hamdan, Samir; El Ali, Bassam

    2016-01-01

    The immobilization of Thermoanaerobacter ethanolicus secondary alcohol dehydrogenase (TeSADH) using sol–gel method enables its use to racemize enantiopure alcohols in organic media. Here, we report the racemization of enantiopure phenyl

  7. Calcium alginate entrapment of the yeast Rhodosporidium toruloides for the kinetic resolution of 1, 2-epoxyoctane

    CSIR Research Space (South Africa)

    Maritz, J

    2003-10-01

    Full Text Available -centrifuge tube. The epoxide substrate was added to give 20 mM in the aqueous phase. The reaction mixtures were incub- ated (20 min, 30 openbulletC) on a shaking water-bath. Liquid samples were removed from the reaction mixtures and the product (R,S-1,2-octanediol...)represent 0.5% (w/v) alginate, the closed squares (squaresolid) 0.75% (w/v) algin- ate, and the closed triangleS (trianglesolid) 1.0% (w/v) alginate concentration combinations. Fig. 8. Repeated batch biotransformation. Twenty percent (w/v) biomass...

  8. High-resolution Hybrid Simulations of Kinetic Plasma Turbulence at Proton Scales

    Czech Academy of Sciences Publication Activity Database

    Franci, L.; Landi, S.; Matteini, L.; Verdini, A.; Hellinger, Petr

    2015-01-01

    Roč. 812, č. 1 (2015), 21/1-21/15 ISSN 0004-637X R&D Projects: GA ČR GA15-10057S Institutional support: RVO:67985815 Keywords : plasmas * solar wind * turbulence Subject RIV: BN - Astronomy, Celestial Mechanics, Astrophysics Impact factor: 5.909, year: 2015

  9. Preparative method for isosilybin isolation based on enzymatic kinetic resolution of silymarin mixture

    Czech Academy of Sciences Publication Activity Database

    Gažák, Radek; Fuksová, Kateřina; Marhol, Petr; Kuzma, Marek; Agarwal, R.; Křen, Vladimír

    2013-01-01

    Roč. 48, č. 1 (2013), s. 184-189 ISSN 1359-5113 R&D Projects: GA ČR GAP207/10/0288; GA MŠk(CZ) ME10027 Institutional support: RVO:61388971 Keywords : Isosilybin * Silymarin * Novozym 435 Subject RIV: CC - Organic Chemistry Impact factor: 2.524, year: 2013

  10. Super-resolution biomolecular crystallography with low-resolution data.

    Science.gov (United States)

    Schröder, Gunnar F; Levitt, Michael; Brunger, Axel T

    2010-04-22

    X-ray diffraction plays a pivotal role in the understanding of biological systems by revealing atomic structures of proteins, nucleic acids and their complexes, with much recent interest in very large assemblies like the ribosome. As crystals of such large assemblies often diffract weakly (resolution worse than 4 A), we need methods that work at such low resolution. In macromolecular assemblies, some of the components may be known at high resolution, whereas others are unknown: current refinement methods fail as they require a high-resolution starting structure for the entire complex. Determining the structure of such complexes, which are often of key biological importance, should be possible in principle as the number of independent diffraction intensities at a resolution better than 5 A generally exceeds the number of degrees of freedom. Here we introduce a method that adds specific information from known homologous structures but allows global and local deformations of these homology models. Our approach uses the observation that local protein structure tends to be conserved as sequence and function evolve. Cross-validation with R(free) (the free R-factor) determines the optimum deformation and influence of the homology model. For test cases at 3.5-5 A resolution with known structures at high resolution, our method gives significant improvements over conventional refinement in the model as monitored by coordinate accuracy, the definition of secondary structure and the quality of electron density maps. For re-refinements of a representative set of 19 low-resolution crystal structures from the Protein Data Bank, we find similar improvements. Thus, a structure derived from low-resolution diffraction data can have quality similar to a high-resolution structure. Our method is applicable to the study of weakly diffracting crystals using X-ray micro-diffraction as well as data from new X-ray light sources. Use of homology information is not restricted to X

  11. Energy resolution of scintillation detectors

    Energy Technology Data Exchange (ETDEWEB)

    Moszyński, M., E-mail: M.Moszynski@ncbj.gov.pl; Syntfeld-Każuch, A.; Swiderski, L.; Grodzicka, M.; Iwanowska, J.; Sibczyński, P.; Szczęśniak, T.

    2016-01-01

    According to current knowledge, the non-proportionality of the light yield of scintillators appears to be a fundamental limitation of energy resolution. A good energy resolution is of great importance for most applications of scintillation detectors. Thus, its limitations are discussed below; which arise from the non-proportional response of scintillators to gamma rays and electrons, being of crucial importance to the intrinsic energy resolution of crystals. The important influence of Landau fluctuations and the scattering of secondary electrons (δ-rays) on intrinsic resolution is pointed out here. The study on undoped NaI and CsI at liquid nitrogen temperature with a light readout by avalanche photodiodes strongly suggests that the non-proportionality of many crystals is not their intrinsic property and may be improved by selective co-doping. Finally, several observations that have been collected in the last 15 years on the influence of the slow components of light pulses on energy resolution suggest that more complex processes are taking place in the scintillators. This was observed with CsI(Tl), CsI(Na), ZnSe(Te), and undoped NaI at liquid nitrogen temperature and, finally, for NaI(Tl) at temperatures reduced below 0 °C. A common conclusion of these observations is that the highest energy resolution, and particularly intrinsic resolution measured with the scintillators, characterized by two or more components of the light pulse decay, is obtainable when the spectrometry equipment integrates the whole light of the components. In contrast, the slow components observed in many other crystals degrade the intrinsic resolution. In the limiting case, afterglow could also be considered as a very slow component that spoils the energy resolution. The aim of this work is to summarize all of the above observations by looking for their origin.

  12. Mass independent kinetic energy reducing inlet system for vacuum environment

    Science.gov (United States)

    Reilly, Peter T. A. [Knoxville, TN

    2010-12-14

    A particle inlet system comprises a first chamber having a limiting orifice for an incoming gas stream and a micrometer controlled expansion slit. Lateral components of the momentum of the particles are substantially cancelled due to symmetry of the configuration once the laminar flow converges at the expansion slit. The particles and flow into a second chamber, which is maintained at a lower pressure than the first chamber, and then moves into a third chamber including multipole guides for electromagnetically confining the particle. The vertical momentum of the particles descending through the center of the third chamber is minimized as an upward stream of gases reduces the downward momentum of the particles. The translational kinetic energy of the particles is near-zero irrespective of the mass of the particles at an exit opening of the third chamber, which may be advantageously employed to provide enhanced mass resolution in mass spectrometry.

  13. Kinetic analysis of pulsed laser induced phosphorescence for uranium determination

    International Nuclear Information System (INIS)

    Serdeiro, Nelida H.

    2003-01-01

    The laser induced kinetic phosphorescence allows the uranium determination in different kind of matrices, with a lower detection limit than those reached by other spectroscopic methods. It involves the uranyl ions excitation by a pulsed dye-laser source, followed by temporal resolution of the phosphorescence. This method is used for the determination of trace quantities of uranium in aqueous solution, with a suitable complexant agent, without chemical separation before the analysis. The objective of this paper is to present the results of uranium determinations in different standard samples, water, soil, filter and urine, and a comparison with other methods such as fluorimetry, alpha spectrometry and mass spectrometry. Moreover, the measurement conditions, the advantages and disadvantages, the sample preparation, the interferences and the detection limit are described. (author)

  14. Microstructure and hydrogen sorption kinetics of Mg nanopowders with catalyst

    International Nuclear Information System (INIS)

    Revesz, A.; Fatay, D.; Spassov, T.

    2007-01-01

    MgH 2 powders were ball-milled with and without catalysts (Nb 2 O 5 ) under hydrogen in a high-energy mill for 10 h. Morphological, structural and microstructural characterization of the nanocomposites, including particle and crystallite size distribution were carried out before and after hydrogen absorption. In order to study the above-mentioned microstructural parameters imaging and X-ray scattering techniques (high-resolution X-ray diffractometry) have been employed. The effect of the particle and grain size on the hydriding/dehydriding kinetics of ball-milled MgH 2 + catalyst powders was analyzed. The grain and particle size reduction enhances substantially the hydriding/dehydriding

  15. Kinetics of solid state phase transformations: Measurement and ...

    Indian Academy of Sciences (India)

    Administrator

    heating or cooling rate can also exert a crucial influence on the kinetic outcome is stressed. The kinetic ... A simple and general modelling methodology for understanding the kinetics of ... state is of interest on both basic and applied grounds.

  16. Rethinking wave-kinetic theory applied to zonal flows

    Science.gov (United States)

    Parker, Jeffrey

    2017-10-01

    Over the past two decades, a number of studies have employed a wave-kinetic theory to describe fluctuations interacting with zonal flows. Recent work has uncovered a defect in this wave-kinetic formulation: the system is dominated by the growth of (arbitrarily) small-scale zonal structures. Theoretical calculations of linear growth rates suggest, and nonlinear simulations confirm, that this system leads to the concentration of zonal flow energy in the smallest resolved scales, irrespective of the numerical resolution. This behavior results from the assumption that zonal flows are extremely long wavelength, leading to the neglect of key terms responsible for conservation of enstrophy. A corrected theory, CE2-GO, is presented; it is free of these errors yet preserves the intuitive phase-space mathematical structure. CE2-GO properly conserves enstrophy as well as energy, and yields accurate growth rates of zonal flow. Numerical simulations are shown to be well-behaved and not dependent on box size. The steady-state limit simplifies into an exact wave-kinetic form which offers the promise of deeper insight into the behavior of wavepackets. The CE2-GO theory takes its place in a hierarchy of models as the geometrical-optics reduction of the more complete cumulant-expansion statistical theory CE2. The new theory represents the minimal statistical description, enabling an intuitive phase-space formulation and an accurate description of turbulence-zonal flow dynamics. This work was supported by an NSF Graduate Research Fellowship, a US DOE Fusion Energy Sciences Fellowship, and US DOE Contract Nos. DE-AC52-07NA27344 and DE-AC02-09CH11466.

  17. Rotational and divergent kinetic energy in the mesoscale model ALADIN

    Directory of Open Access Journals (Sweden)

    V. Blažica

    2013-03-01

    Full Text Available Kinetic energy spectra from the mesoscale numerical weather prediction (NWP model ALADIN with horizontal resolution 4.4 km are split into divergent and rotational components which are then compared at horizontal scales below 300 km and various vertical levels. It is shown that about 50% of kinetic energy in the free troposphere in ALADIN is divergent energy. The percentage increases towards 70% near the surface and in the upper troposphere towards 100 hPa. The maximal percentage of divergent energy is found at stratospheric levels around 100 hPa and at scales below 100 km which are not represented by the global models. At all levels, the divergent energy spectra are characterised by shallower slopes than the rotational energy spectra, and the difference increases as horizontal scales become larger. A very similar vertical distribution of divergent energy is obtained by using the standard ALADIN approach for the computation of spectra based on the extension zone and by applying detrending approach commonly used in mesoscale NWP community.

  18. Discrete kinetic models from funneled energy landscape simulations.

    Directory of Open Access Journals (Sweden)

    Nicholas P Schafer

    Full Text Available A general method for facilitating the interpretation of computer simulations of protein folding with minimally frustrated energy landscapes is detailed and applied to a designed ankyrin repeat protein (4ANK. In the method, groups of residues are assigned to foldons and these foldons are used to map the conformational space of the protein onto a set of discrete macrobasins. The free energies of the individual macrobasins are then calculated, informing practical kinetic analysis. Two simple assumptions about the universality of the rate for downhill transitions between macrobasins and the natural local connectivity between macrobasins lead to a scheme for predicting overall folding and unfolding rates, generating chevron plots under varying thermodynamic conditions, and inferring dominant kinetic folding pathways. To illustrate the approach, free energies of macrobasins were calculated from biased simulations of a non-additive structure-based model using two structurally motivated foldon definitions at the full and half ankyrin repeat resolutions. The calculated chevrons have features consistent with those measured in stopped flow chemical denaturation experiments. The dominant inferred folding pathway has an "inside-out", nucleation-propagation like character.

  19. Modeling of subtle kinetic processes in plasma simulation

    International Nuclear Information System (INIS)

    Sydora, R.D.; Decyk, V.K.; Dawson, J.M.

    1988-01-01

    A new diagnostic method for plasma simulation models is presented which enables one to probe the subtle dielectric properties of the plasma medium. The procedure involves the removal of the background plasma response in order to isolate the effects of small perturbing influences which are externally added. We have found the technique accurately describes fundamental kinetic plasma behavior such as the shielding of individual test charges and currents. Wave emission studies and drag of test particles has been carried out in explicit particle algorithms as well as large time step implicit and gyrokinetic models. Accurate plasma behavior is produced and it is possible to investigate in detail, processes which can be compared with plasma kinetic theory. The technique of subtraction is not only limited to particle simulation models but also can be used in MHD or fluid models where resolution is difficult due to the intensity of the background response relative to the phenomena one is interested in measuring, such as a weakly grouwing instability or nonlinear mode coupling effect. (author)

  20. The cerebellum mediates conflict resolution.

    Science.gov (United States)

    Schweizer, Tom A; Oriet, Chris; Meiran, Nachshon; Alexander, Michael P; Cusimano, Michael; Stuss, Donald T

    2007-12-01

    Regions within the frontal and parietal cortex have been implicated as important neural correlates for cognitive control during conflict resolution. Despite the extensive reciprocal connectivity between the cerebellum and these putatively critical cortical areas, a role for the cerebellum in conflict resolution has never been identified. We used a task-switching paradigm that separates processes related to task-set switching and the management of response conflict independent of motor processing. Eleven patients with chronic, focal lesions to the cerebellum and 11 healthy controls were compared. Patients were slower and less accurate in conditions involving conflict resolution. In the absence of response conflict, however, tasks-witching abilities were not impaired in our patients. The cerebellum may play an important role in coordinating with other areas of cortex to modulate active response states. These results are the first demonstration of impaired conflict resolution following cerebellar lesions in the presence of an intact prefrontal cortex.