Science.gov

Sample records for active reaction centers

  1. Photosynthetic Reaction Centers as Active Molecular Electronic Components. Phase I

    DTIC Science & Technology

    1993-08-13

    lauryl dimethylarnine oxide (LDAO). This is followed by final purification by ion-exchange chromatography. Typical media are DEAE-Sephacel with an...producing improved forms of subtilisin which is widely used in laundry detergents. Other more direct routes to stabilizing the protein structure...purified reaction centers will allow us to eliminate the extraction steps in the purification procedure which are associated with removing the antenna

  2. Substrate activation for O2 reactions by oxidized metal centers in biology.

    PubMed

    Pau, Monita Y M; Lipscomb, John D; Solomon, Edward I

    2007-11-20

    The uncatalyzed reactions of O(2) (S = 1) with organic substrates (S = 0) are thermodynamically favorable but kinetically slow because they are spin-forbidden and the one-electron reduction potential of O(2) is unfavorable. In nature, many of these important O(2) reactions are catalyzed by metalloenzymes. In the case of mononuclear non-heme iron enzymes, either Fe(II) or Fe(III) can play the catalytic role in these spin-forbidden reactions. Whereas the ferrous enzymes activate O(2) directly for reaction, the ferric enzymes activate the substrate for O(2) attack. The enzyme-substrate complex of the ferric intradiol dioxygenases exhibits a low-energy catecholate to Fe(III) charge transfer transition that provides a mechanism by which both the Fe center and the catecholic substrate are activated for the reaction with O(2). In this Perspective, we evaluate how the coupling between this experimentally observed charge transfer and the change in geometry and ligand field of the oxidized metal center along the reaction coordinate can overcome the spin-forbidden nature of the O(2) reaction.

  3. Activation Strain Analysis of SN2 Reactions at C, N, O, and F Centers.

    PubMed

    Kubelka, Jan; Bickelhaupt, F Matthias

    2017-02-02

    Fundamental principles that determine chemical reactivity and reaction mechanisms are the very foundation of chemistry and many related fields of science. Bimolecular nucleophilic substitutions (SN2) are among the most common and therefore most important reaction types. In this report, we examine the trends in the SN2 reactions with respect to increasing electronegativity of the reaction center by comparing the well-studied backside SN2 Cl(-) + CH3Cl with similar Cl(-) substitutions on the isoelectronic series with the second period elements N, O, and F in place of C. Relativistic (ZORA) DFT calculations are used to construct the gas phase reaction potential energy surfaces (PES), and activation strain analysis, which allows decomposition of the PES into the geometrical strain and interaction energy, is employed to analyze the observed trends. We find that SN2@N and SN2@O have similar PES to the prototypical SN2@C, with the well-defined reaction complex (RC) local minima and a central barrier, but all stationary points are, respectively, increasingly stable in energy. The SN2@F, by contrast, exhibits only a single-well PES with no barrier. Using the activation strain model, we show that the trends are due to the interaction energy and originate mainly from the decreasing energy of the empty acceptor orbital (σ*A-Cl) on the reaction center A in the order of C, N, O, and F. The decreasing steric congestion around the central atom is also a likely contributor to this trend. Additional decomposition of the interaction energy using Kohn-Sham molecular orbital (KS-MO) theory provides further support for this explanation, as well as suggesting electrostatic energy as the primary reason for the distinct single-well PES profile for the FCl reaction.

  4. Activation Strain Analysis of SN2 Reactions at C, N, O, and F Centers

    PubMed Central

    2017-01-01

    Fundamental principles that determine chemical reactivity and reaction mechanisms are the very foundation of chemistry and many related fields of science. Bimolecular nucleophilic substitutions (SN2) are among the most common and therefore most important reaction types. In this report, we examine the trends in the SN2 reactions with respect to increasing electronegativity of the reaction center by comparing the well-studied backside SN2 Cl– + CH3Cl with similar Cl– substitutions on the isoelectronic series with the second period elements N, O, and F in place of C. Relativistic (ZORA) DFT calculations are used to construct the gas phase reaction potential energy surfaces (PES), and activation strain analysis, which allows decomposition of the PES into the geometrical strain and interaction energy, is employed to analyze the observed trends. We find that SN2@N and SN2@O have similar PES to the prototypical SN2@C, with the well-defined reaction complex (RC) local minima and a central barrier, but all stationary points are, respectively, increasingly stable in energy. The SN2@F, by contrast, exhibits only a single-well PES with no barrier. Using the activation strain model, we show that the trends are due to the interaction energy and originate mainly from the decreasing energy of the empty acceptor orbital (σ*A–Cl) on the reaction center A in the order of C, N, O, and F. The decreasing steric congestion around the central atom is also a likely contributor to this trend. Additional decomposition of the interaction energy using Kohn–Sham molecular orbital (KS-MO) theory provides further support for this explanation, as well as suggesting electrostatic energy as the primary reason for the distinct single-well PES profile for the FCl reaction. PMID:28045531

  5. [High activity antiretroviral therapy change associated to adverse drug reactions in a specialized center in Venezuela].

    PubMed

    Subiela, José D; Dapena, Elida

    2016-03-01

    Adverse drug reactions (ADRs) represent the first cause of change of the first-line highly active antiretroviral therapy (HAART) regimen, therefore, they constitute the main limiting factor in the long-term follow up of HIV patients in treatment. A retrospective study was carried out in a specialized center in Lara State, Venezuela, including 99 patients over 18 years of age who had change of first-line HAART regimen due to ADRs, between 2010 and 2013. The aims of this research were to describe the sociodemographic and clinical variables, frequency of ADRs related to change of HAART, duration of the first-line HAART regimen, to determine the drugs associated with ARVs and to identify the risk factors. The ADRs constituted 47.5% of all causes of change of first-line HAART regimen, the median duration was 1.08±0.28 years. The most frequent ADRs were anemia (34.3%), hypersensitivity reactions (20.2%) and gastrointestinal intolerance (13.1%). The most frequent ARV regimen type was the protease inhibitors-based regimen (59.6%), but zidovudine was the ARV most linked to ADRs (41.4%). The regression analysis showed increased risk of ADRs in singles and students in the univariate analysis and heterosexuals and homosexuals in multivariate analysis; and decreased risk in active workers. The present work shows the high prevalence of ADRs in the studied population and represents the first case-based study that describes the pharmacoepidemiology of a cohort of HIV-positive patients treated in Venezuela.

  6. Versatility of biological non-heme Fe(II) centers in oxygen activation reactions

    PubMed Central

    Kovaleva, Elena G; Lipscomb, John D

    2009-01-01

    Oxidase and oxygenase enzymes allow the use of relatively unreactive O2 in biochemical reactions. Many of the mechanistic strategies employed in nature for this key reaction are represented within the 2-His-1-carboxylate facial triad family of non-heme Fe(II) containing enzymes. The open face of the metal coordination sphere opposite the three endogenous ligands participates directly in the reaction chemistry. Here, data from several studies are presented showing that reductive O2 activation within this family is initiated by substrate (and in some cases co-substrate or cofactor) binding, which then allows coordination of O2 to the metal. From this starting point, both the O2 activation process and the reactions with substrates diverge broadly. The reactive species formed in these reactions have been proposed to encompass four oxidation states of iron and all forms of reduced O2 as well as several of the reactive oxygen species that derive from O–O bond cleavage. PMID:18277980

  7. Regional Planning: Focus on the Toronto-Centered Plan, Implications and Reactions. Instructional Activities Series IA/S-3.

    ERIC Educational Resources Information Center

    Addison, William S.

    This activity is one of a series of 17 teacher-developed instructional activities for geography at the secondary-grade level described in SO 009 140. This activity is a report or case study which looks at the implications, problems, and reactions to a regional comprehensive plan to regulate growth patterns in a 15,000 square-mile area of Toronto,…

  8. Site energies of active and inactive pheophytins in the reaction center of Photosystem II from Chlamydomonas reinhardtii.

    PubMed

    Acharya, K; Neupane, B; Zazubovich, V; Sayre, R T; Picorel, R; Seibert, M; Jankowiak, R

    2012-03-29

    It is widely accepted that the primary electron acceptor in various Photosystem II (PSII) reaction center (RC) preparations is pheophytin a (Pheo a) within the D1 protein (Pheo(D1)), while Pheo(D2) (within the D2 protein) is photochemically inactive. The Pheo site energies, however, have remained elusive, due to inherent spectral congestion. While most researchers over the past two decades placed the Q(y)-states of Pheo(D1) and Pheo(D2) bands near 678-684 and 668-672 nm, respectively, recent modeling [Raszewski et al. Biophys. J. 2005, 88, 986 - 998; Cox et al. J. Phys. Chem. B 2009, 113, 12364 - 12374] of the electronic structure of the PSII RC reversed the assignment of the active and inactive Pheos, suggesting that the mean site energy of Pheo(D1) is near 672 nm, whereas Pheo(D2) (~677.5 nm) and Chl(D1) (~680 nm) have the lowest energies (i.e., the Pheo(D2)-dominated exciton is the lowest excited state). In contrast, chemical pigment exchange experiments on isolated RCs suggested that both pheophytins have their Q(y) absorption maxima at 676-680 nm [Germano et al. Biochemistry 2001, 40, 11472 - 11482; Germano et al. Biophys. J. 2004, 86, 1664 - 1672]. To provide more insight into the site energies of both Pheo(D1) and Pheo(D2) (including the corresponding Q(x) transitions, which are often claimed to be degenerate at 543 nm) and to attest that the above two assignments are most likely incorrect, we studied a large number of isolated RC preparations from spinach and wild-type Chlamydomonas reinhardtii (at different levels of intactness) as well as the Chlamydomonas reinhardtii mutant (D2-L209H), in which the active branch Pheo(D1) is genetically replaced with chlorophyll a (Chl a). We show that the Q(x)-/Q(y)-region site energies of Pheo(D1) and Pheo(D2) are ~545/680 nm and ~541.5/670 nm, respectively, in good agreement with our previous assignment [Jankowiak et al. J. Phys. Chem. B 2002, 106, 8803 - 8814]. The latter values should be used to model excitonic

  9. Site Energies of Active and Inactive Pheophytins in the Reaction Center of Photosystem II from Chlamydomonas Reinhardtii

    SciTech Connect

    Acharya, K.; Neupane, B.; Zazubovich, V.; Sayre, R. T.; Picorel, R.; Seibert, M.; Jankowiak, R.

    2012-03-29

    It is widely accepted that the primary electron acceptor in various Photosystem II (PSII) reaction center (RC) preparations is pheophytin {alpha} (Pheo {alpha}) within the D1 protein (Pheo{sub D1}), while Pheo{sub D2} (within the D2 protein) is photochemically inactive. The Pheo site energies, however, have remained elusive, due to inherent spectral congestion. While most researchers over the past two decades placed the Q{sub y}-states of Pheo{sub D1} and Pheo{sub D2} bands near 678-684 and 668-672 nm, respectively, recent modeling [Raszewski et al. Biophys. J. 2005, 88, 986-998; Cox et al. J. Phys. Chem. B 2009, 113, 12364-12374] of the electronic structure of the PSII RC reversed the assignment of the active and inactive Pheos, suggesting that the mean site energy of Pheo{sub D1} is near 672 nm, whereas Pheo{sub D2} ({approx}677.5 nm) and Chl{sub D1} ({approx}680 nm) have the lowest energies (i.e., the Pheo{sub D2}-dominated exciton is the lowest excited state). In contrast, chemical pigment exchange experiments on isolated RCs suggested that both pheophytins have their Q{sub y} absorption maxima at 676-680 nm [Germano et al. Biochemistry 2001, 40, 11472-11482; Germano et al. Biophys. J. 2004, 86, 1664-1672]. To provide more insight into the site energies of both Pheo{sub D1} and Pheo{sub D2} (including the corresponding Q{sub x} transitions, which are often claimed to be degenerate at 543 nm) and to attest that the above two assignments are most likely incorrect, we studied a large number of isolated RC preparations from spinach and wild-type Chlamydomonas reinhardtii (at different levels of intactness) as well as the Chlamydomonas reinhardtii mutant (D2-L209H), in which the active branch Pheo{sub D1} is genetically replaced with chlorophyll {alpha} (Chl {alpha}). We show that the Q{sub x}-/Q{sub y}-region site energies of Pheo{sub D1} and Pheo{sub D2} are {approx}545/680 nm and {approx}541.5/670 nm, respectively, in good agreement with our previous assignment

  10. Photosynthetic reaction center complexes from heliobacteria

    NASA Technical Reports Server (NTRS)

    Trost, J. T.; Vermaas, W. F. J.; Blankenship, R. E.

    1991-01-01

    The goal of this project is to understand the early evolutionary development of photosynthesis by examining the properties of reaction centers isolated from certain contemporary organisms that appear to contain the simplest photosynthetic reaction centers. The major focus of this project is the family of newly discovered strictly anaerobic photosynthetic organisms known as Heliobacteria. These organisms are the only known photosynthetic organisms that are grouped with the gram-positive phylum of bacteria. The properties of these reaction centers suggest that they might be the decendants of an ancestor that also gave rise to Photosystem 1 found in oxygen-evolving photosynthetic organisms. Photoactive reaction center-core antenna complexes have been isolated from the photosynthetic bacteria Heliobacillus mobilis and Heliobacterium gestii. The absorption and fluorescence properties of membranes and reaction centers are almost identical, suggesting that a single pigment-protein complex serves as both antenna and reaction center. Experiments in progress include sequence determination of the 48,000 Mr reaction center protein, and evolutionary comparisons with other reaction center proteins.

  11. Photosynthetic reaction center complexes from heliobacteria

    NASA Technical Reports Server (NTRS)

    Trost, J. T.; Vermaas, W. F. J.; Blankenship, R. E.

    1991-01-01

    Photosynthetic reaction centers are pigment-protein complexes that are responsible for the transduction of light energy into chemical energy. Considerable evidence indicates that photosynthetic organisms were present very early in the evolution of life on Earth. The goal of this project is to understand the early evolutionary development of photosynthesis by examining the properties of reaction centers isolated from certain contemporary organisms that appear to contain the simplest photosynthetic reaction centers. The major focus is on the family of newly discovered strictly anaerobic photosynthetic organisms that are grouped with the gram-positive phylum of bacteria. The properties of these reactions centers suggest that they may be the descendants of an ancestor that also gave rise to Photosystem 1 found in oxygen-evolving photosynthetic organisms. Photoactive reaction center-core antenna complexes were isolated from the photosynthetic bacteria, Heliobacillus mobilis and Heliobacterium gestii, by extraction of membranes with Deriphat 160C followed by differential centrifugation and sucrose density gradient centrifugation. Other aspects of this investigation are briefly discussed.

  12. Design of dinuclear manganese cofactors for bacterial reaction centers.

    PubMed

    Olson, Tien L; Espiritu, Eduardo; Edwardraja, Selvakumar; Simmons, Chad R; Williams, JoAnn C; Ghirlanda, Giovanna; Allen, James P

    2016-05-01

    A compelling target for the design of electron transfer proteins with novel cofactors is to create a model for the oxygen-evolving complex, a Mn4Ca cluster, of photosystem II. A mononuclear Mn cofactor can be added to the bacterial reaction center, but the addition of multiple metal centers is constrained by the native protein architecture. Alternatively, metal centers can be incorporated into artificial proteins. Designs for the addition of dinuclear metal centers to four-helix bundles resulted in three artificial proteins with ligands for one, two, or three dinuclear metal centers able to bind Mn. The three-dimensional structure determined by X-ray crystallography of one of the Mn-proteins confirmed the design features and revealed details concerning coordination of the Mn center. Electron transfer between these artificial Mn-proteins and bacterial reaction centers was investigated using optical spectroscopy. After formation of a light-induced, charge-separated state, the experiments showed that the Mn-proteins can donate an electron to the oxidized bacteriochlorophyll dimer of modified reaction centers, with the Mn-proteins having additional metal centers being more effective at this electron transfer reaction. Modeling of the structure of the Mn-protein docked to the reaction center showed that the artificial protein likely binds on the periplasmic surface similarly to cytochrome c2, the natural secondary donor. Combining reaction centers with exogenous artificial proteins provides the opportunity to create ligands and investigate the influence of inhomogeneous protein environments on multinuclear redox-active metal centers. This article is part of a Special Issue entitled Biodesign for Bioenergetics--the design and engineering of electronic transfer cofactors, proteins and protein networks, edited by Ronald L. Koder and J.L. Ross Anderson.

  13. Origin and evolution of photosynthetic reaction centers

    NASA Astrophysics Data System (ADS)

    Olson, John M.; Pierson, Beverly K.

    1987-09-01

    The prototype reaction center may have used protoporphyrin-IX associated with small peptides to transfer electrons or protons across the primitive cell membrane. The precursor of all contemporary reaction centers contained chlorophylla molecules as both primary electron donor and initial electron acceptor and an Fe-S center as secondary acceptor (RC-1 type). The biosynthetic pathway for chlorophylla evolved along with the evolution of a better organized reaction center associated with cytochromes and quinones in a primitive cyclic electron transport system. This reaction center probably functioned initially in photoassimilation, but was easily adapted to CO2 fixation using H2 and H2S as reductants. During this phase bacteriochlorophyllg may have evolved from chlorophylla in response to competition for light, and thereby initiated the gram-positive line of eubacteria. A second reaction center (RC-2) evolved from RC-1 between 3.5 and 2.5 Ga ago in response to the competition for reductants for CO2 fixation. The new organism containing RC-2 in series with RC-1 would have been able to use poor reducing agents such as the abundant aqueous ferrous ion in place of H2 and H2S. This new organism is proposed to be the common ancestor of all phototrophic eubacteria except those related to the gram-positive bacteria. All organisms containing bacteriochlorophylla lost either RC-1 or RC-2, while those organisms containing chlorophylla (ancestors of cyanobacteria) added a water-splitting enzyme to RC-2 between 3.0 and 2.5 Ga ago in order to use H2O in place of hydrated ferrous ion as electron donor for autotrophic photosynthesis.

  14. Photo-CIDNP of Photosyntheitc Reaction Centers

    SciTech Connect

    Ann. E. McDermott

    2005-10-22

    Studies of Photochemically Induced Dynamic Nuclear Polarization in Photosynthetic Bacterial Reaction Centers: Wavelength and Time Dependence Solid-state NMR spectra of quinone-reduced photosynthetic bacterial reaction centers (RCs) and chromatophores exhibit certain strongly enhanced lines under illumination, a result of photochemically induced dynamic nuclear polarization (photo-CIDNP). This technique offers a new method to investigate photosynthetic electronic transactions while retaining the NMR advantages of narrow linewidths and site-specific resolution. Pulsed laser illumination at 532 nm was used as the basis for time resolved photo-CIDNP experiments, a technique not previously published for solid-state photosynthetic systems. These measurements offer insight about the origin of the polarization effects.

  15. Structural, kinetic, and theoretical studies on models of the zinc-containing phosphodiesterase active center: medium-dependent reaction mechanisms.

    PubMed

    Selmeczi, Katalin; Michel, Carine; Milet, Anne; Gautier-Luneau, Isabelle; Philouze, Christian; Pierre, Jean-Louis; Schnieders, David; Rompel, Annette; Belle, Catherine

    2007-01-01

    Dinuclear zinc(II) complexes [Zn(2)(bpmp)(mu-OH)](ClO(4))(2) (1) and [Zn(2)(bpmp)(H(2)O)(2)](ClO(4))(3) (2) (H-BPMP=2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol) have been synthesized, structurally characterized, and pH-driven changes in metal coordination observed. The transesterification reaction of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) in the presence of the two complexes was studied both in a water/DMSO (70:30) mixture and in DMSO. Complex 2 was not reactive whereas for 1 considerable rate enhancement of the spontaneous hydrolysis reaction was observed. A detailed mechanistic investigation by kinetic studies, spectroscopic measurements ((1)H, (31)P NMR spectroscopy), and ESI-MS analysis in conjunction with ab initio calculations was performed on 1. Based on these results, two medium-dependent mechanisms are presented and an unusual bridging phosphate intermediate is proposed for the process in DMSO.

  16. Distributed Active Archive Center

    NASA Technical Reports Server (NTRS)

    Bodden, Lee; Pease, Phil; Bedet, Jean-Jacques; Rosen, Wayne

    1993-01-01

    The Goddard Space Flight Center Version 0 Distributed Active Archive Center (GSFC V0 DAAC) is being developed to enhance and improve scientific research and productivity by consolidating access to remote sensor earth science data in the pre-EOS time frame. In cooperation with scientists from the science labs at GSFC, other NASA facilities, universities, and other government agencies, the DAAC will support data acquisition, validation, archive and distribution. The DAAC is being developed in response to EOSDIS Project Functional Requirements as well as from requirements originating from individual science projects such as SeaWiFS, Meteor3/TOMS2, AVHRR Pathfinder, TOVS Pathfinder, and UARS. The GSFC V0 DAAC has begun operational support for the AVHRR Pathfinder (as of April, 1993), TOVS Pathfinder (as of July, 1993) and the UARS (September, 1993) Projects, and is preparing to provide operational support for SeaWiFS (August, 1994) data. The GSFC V0 DAAC has also incorporated the existing data, services, and functionality of the DAAC/Climate, DAAC/Land, and the Coastal Zone Color Scanner (CZCS) Systems.

  17. Light saturation response of inactive photosystem II reaction centers in spinach.

    PubMed

    Chylla, R A; Whitmarsh, J

    1990-07-01

    The effective absorption cross section of inactive photosystem II (PS II) centers, which is the product of the effective antenna size and the quantum yield for photochemistry, was investigated by comparing the light saturation curves of inactive PS II and active reaction centers in intact chloroplasts and thylakoid membranes of spinach (Spinacia oleracea). Inactive PS II centers are defined as the impaired PS II reaction centers that require greater than 50 ms for the reoxidation of QA (-) subsequent to a single turnover flash. Active reaction centers are defined as the rapidly turning over PS II centers (recovery time less than 50 ms) and all of the PS I centers. The electrochromic shift, measured by the flash-induced absorbance increase at 518 nm, was used to probe the activity of the reaction centers. Light saturation curves were generated for inactive PS II centers and active reaction centers by measuring the extent of the absorbance increase at 518 nm induced by red actinic flashes of variable energy. The light saturation curves show that inactive PS II centers required over twice as many photons as active reaction centers to achieve the same yield. The ratio of the flash energy required for 50% saturation for active reaction centers (PS II active + PS I) compared to inactive PS II centers was 0.45±0.04 in intact chloroplasts, and 0.54±0.11 in thylakoid membranes. Analysis of the light saturation curves using a Poisson statistical model in which the ratio of the antenna size of active PS II centers to that of PS I is considered to range from 1 to 1.5, indicates that the effective absorption cross section of inactive PS II centers was 0.54-0.37 times that of active PS II centers. If the quantum yield for photochemistry is assumed to be one, we estimate that the antenna system serving the inactive PS II centers contains approx. 110 chlorophyll molecules.

  18. Multiantenna artificial photosynthetic reaction center complex.

    PubMed

    Terazono, Yuichi; Kodis, Gerdenis; Liddell, Paul A; Garg, Vikas; Moore, Thomas A; Moore, Ana L; Gust, Devens

    2009-05-21

    In order to ensure efficient utilization of the solar spectrum, photosynthetic organisms use a variety of antenna chromophores to absorb light and transfer excitation to a reaction center, where photoinduced charge separation occurs. Reported here is a synthetic molecular heptad that features two bis(phenylethynyl)anthracene and two borondipyrromethene antennas linked to a hexaphenylbenzene core that also bears two zinc porphyrins. A fullerene electron acceptor self-assembles to both porhyrins via dative bonds. Excitation energy is transferred very efficiently from all four antennas to the porphyrins. Singlet-singlet energy transfer occurs both directly and by a stepwise funnel-like pathway wherein excitation moves down a thermodynamic gradient. The porphyrin excited states donate an electron to the fullerene with a time constant of 3 ps to generate a charge-separated state with a lifetime of 230 ps. The overall quantum yield is close to unity. In the absence of the fullerene, the porphyrin excited singlet state donates an electron to a borondipyrromethene on a slower time scale. This molecule demonstrates that by incorporating antennas, it is possible for a molecular system to harvest efficiently light throughout the visible from ultraviolet wavelengths out to approximately 650 nm.

  19. The role played by acid and basic centers in the activity of biomimetic catalysts of the catalase, peroxidase, and monooxidase reactions

    NASA Astrophysics Data System (ADS)

    Magerramov, A. M.; Nagieva, I. T.

    2010-11-01

    The acid-basic centers of heterogeneous carriers of catalase, peroxidase, and monooxigenase biomimetics, in particular, iron protoporphyrin deposited on active or neutral aluminum magnesium silicate, were studied. The catalytic activity of biomimetics was stabilized, which allowed us not only to synthesize fairly effective biomimetics but also to clarify certain details of the mechanism of their action and perform a comparative analysis of the functioning of biomimetics and the corresponding enzymes.

  20. Characterization of photosynthetic reaction centers by surface-enhanced resonance Raman scattering

    NASA Astrophysics Data System (ADS)

    Chumanov, George D.; Cotton, Therese M.; Zhou, Chengli; Gaul, Dale; Picorel, Rafael; Seibert, Michael

    1993-06-01

    Surface-enhanced Resonance Raman scattering (SERRS) spectra were obtained for the reaction center complexes of the photosynthetic bacterium Rhodobacter sphaeroides (RC) and from photosystem II (PSII) of spinach, adsorbed on Ag and Au surfaces. These preliminary results demonstrate the considerable potential of this technique for selectively exciting resonance Raman scattering from reaction center components within their distinct absorption bands. Because of the high sensitivity afforded by SERRS, spectra could be measured from a single monolayer of reaction centers adsorbed on a metal surface. The surface-sensitivity provides new information indicating the topology of the PSII reaction center 47 kD light-harvesting protein complex. The activity of the PSII reaction center complex adsorbed on metal surfaces was monitored by photochemical reduction of cyt b-559. Measurement of fluorescence emission was shown to be a new and sensitive method for monitoring the structural and functional integrity of the PSII reaction center complex on the metal surface.

  1. Conformationally Constrained Macrocyclic Diporphyrin-Fullerene Artificial Photosynthetic Reaction Center

    PubMed Central

    Garg, Vikas; Kodis, Gerdenis; Chachisvilis, Mirianas; Hambourger, Michael; Moore, Ana L.; Moore, Thomas A.; Gust, Devens

    2011-01-01

    Photosynthetic reaction centers convert excitation energy from absorbed sunlight into chemical potential energy in the form of a charge-separated state. The rates of the electron transfer reactions necessary to achieve long-lived, high-energy charge-separated states with high quantum yields are determined in part by precise control of the electronic coupling among the chromophores, donors and acceptors, and of the reaction energetics. Successful artificial photosynthetic reaction centers for solar energy conversion have similar requirements. Control of electronic coupling in particular necessitates chemical linkages between active component moieties that both mediate coupling and restrict conformational mobility so that only spatial arrangements that promote favorable coupling are populated. Toward this end, we report the synthesis, structure and photochemical properties of an artificial reaction center containing two porphyrin electron donor moieties and a fullerene electron acceptor in a macrocyclic arrangement involving a ring of 42 atoms. The two porphyrins are closely spaced, in an arrangement reminiscent of that of the special pair in bacterial reaction centers. The molecule is produced by an unusual cyclization reaction that yields mainly a product with C2 symmetry and trans-2 disubstitution at the fullerene. The macrocycle maintains a rigid, highly-constrained structure that was determined by UV-vis spectroscopy, NMR, mass spectrometry, and molecular modeling at the semi-empirical PM6 and DFT (B3LYP/6-31G**) levels. Transient absorption results for the macrocycle in 2-methyltetrahydrofuran reveal photoinduced electron transfer from the porphyrin first excited singlet state to the fullerene to form a P•+-C60•−-P charge separated state with a time constant of 1.1 ps. Photoinduced electron transfer to the fullerene excited singlet state to form the same charge-separated state has a time constant of 15 ps. The charge-separated state is formed with a

  2. Student-Centered Reading Activities.

    ERIC Educational Resources Information Center

    Moffett, James; Wagner, Betty Jane

    1991-01-01

    Offers student-centered reading activities designed to bring students to reading maturity and involvement in literature. Discusses partner reading, dramatizing and performing texts, transforming texts, journal writing, discussion, and writing. (PRA)

  3. Evolution of a reaction center in an explosive material

    NASA Technical Reports Server (NTRS)

    Jackson, T. L.; Kapila, A. K.; Stewart, D. S.

    1989-01-01

    Consideration is given to the spatial structure and temporal evolution of a reaction center for a model involving Arrhenius kinetics. The center, which is characterized by peaks in pressure and temperature with little diminution in local density, is found to have one of two possible self-similar structures. The analysis uses a combination of asymptotics and numerics and terminates when pressure and temperature in the reaction center have peaked.

  4. Quantum oscillatory exciton migration in photosynthetic reaction centers

    NASA Astrophysics Data System (ADS)

    Abramavicius, Darius; Mukamel, Shaul

    2010-08-01

    The harvesting of solar energy and its conversion to chemical energy is essential for all forms of life. The primary photon absorption, transport, and charge separation events, which trigger a chain of chemical reactions, take place in membrane-bound photosynthetic complexes. Whether quantum effects, stemming from entanglement of chromophores, persist in the energy transport at room temperature, despite the rapid decoherence effects caused by environment fluctuations, is under current active debate. If confirmed, these may explain the high efficiency of light harvesting and open up numerous applications to quantum computing and information processing. We present simulations of the photosynthetic reaction center of photosystem II that clearly establish oscillatory energy transport at room temperature originating from interference of quantum pathways. These signatures of quantum transport may be observed by two dimensional coherent optical spectroscopy.

  5. Quantum oscillatory exciton migration in photosynthetic reaction centers.

    PubMed

    Abramavicius, Darius; Mukamel, Shaul

    2010-08-14

    The harvesting of solar energy and its conversion to chemical energy is essential for all forms of life. The primary photon absorption, transport, and charge separation events, which trigger a chain of chemical reactions, take place in membrane-bound photosynthetic complexes. Whether quantum effects, stemming from entanglement of chromophores, persist in the energy transport at room temperature, despite the rapid decoherence effects caused by environment fluctuations, is under current active debate. If confirmed, these may explain the high efficiency of light harvesting and open up numerous applications to quantum computing and information processing. We present simulations of the photosynthetic reaction center of photosystem II that clearly establish oscillatory energy transport at room temperature originating from interference of quantum pathways. These signatures of quantum transport may be observed by two dimensional coherent optical spectroscopy.

  6. Pigment exchange of photosystem II reaction center by chlorophyll d.

    PubMed

    Tomo, Tatsuya; Hirano, Emi; Nagata, Junko; Nakazato, Katsuyoshi

    2005-06-01

    Pigment exchanges among photosystem reaction centers (RCs) are useful for the identification and functional analysis of chromophores in photosynthetic organisms. Pigment replacement within the spinach Photosystem II RC was performed with Chl d derived from the oxygenic alga Acaryochloris marina, using a protocol similar to that reported previously [Gall et al. (1998) FEBS Lett 434: 88-92] based on the incubation of reaction centers with an excess of other pigments. In this study, we analyzed Chl d-modified monomeric RC which was separated from Chl d-modified dimeric RC by size-exclusion chromatography. Based on the assumption of a constant ratio of two Pheo a molecules per RC, the number of Chl a molecules in Chl d-modified monomeric RCs was found to decrease from six to four. The absorption spectrum of the Chl d-modified monomeric RC at room temperature showed a large peak at 699.5 nm originating from Chl d and a small peak at 672.5 nm orignating from Chl a. Photoaccumulation of the Pheo a- in Chl d-modified monomeric RC, in the presence of sodium dithionate and methyl viologen, did not differ significantly from that in control RC, showing that the Chl d-modified monomeric RC retains its charge separation activity and photochemically active Pheo a.

  7. Bio-Photoelectrochemical Solar Cells Incorporating Reaction Center and Reaction Center Plus Light Harvesting Complexes

    NASA Astrophysics Data System (ADS)

    Yaghoubi, Houman

    Harvesting solar energy can potentially be a promising solution to the energy crisis now and in the future. However, material and processing costs continue to be the most important limitations for the commercial devices. A key solution to these problems might lie within the development of bio-hybrid solar cells that seeks to mimic photosynthesis to harvest solar energy and to take advantage of the low material costs, negative carbon footprint, and material abundance. The bio-photoelectrochemical cell technologies exploit biomimetic means of energy conversion by utilizing plant-derived photosystems which can be inexpensive and ultimately the most sustainable alternative. Plants and photosynthetic bacteria harvest light, through special proteins called reaction centers (RCs), with high efficiency and convert it into electrochemical energy. In theory, photosynthetic RCs can be used in a device to harvest solar energy and generate 1.1 V open circuit voltage and ~1 mA cm-2 short circuit photocurrent. Considering the nearly perfect quantum yield of photo-induced charge separation, efficiency of a protein-based solar cell might exceed 20%. In practice, the efficiency of fabricated devices has been limited mainly due to the challenges in the electron transfer between the protein complex and the device electrodes as well as limited light absorption. The overarching goal of this work is to increase the power conversion efficiency in protein-based solar cells by addressing those issues (i.e. electron transfer and light absorption). This work presents several approaches to increase the charge transfer rate between the photosynthetic RC and underlying electrode as well as increasing the light absorption to eventually enhance the external quantum efficiency (EQE) of bio-hybrid solar cells. The first approach is to decrease the electron transfer distance between one of the redox active sites in the RC and the underlying electrode by direct attachment of the of protein complex

  8. Immobilization of photosynthetic reaction centers on metal surfaces

    SciTech Connect

    Cotton, T.M.; Chumanov, G.; Gual, D.

    1993-12-31

    Membrane-bound proteins are ideal candidates for immobilization on surfaces because of their distinct hydrophobic and hydrophilic regions. Their interaction with a particular surface should depend upon its hydrophilicity. Variation of the surface properties is expected to result in changes in the orientation of an absorbed protein. In this study, two methods for immobilization of reaction centers from Rhodobacter sphaeroids on metal surfaces have been compared, including self-assembly or spontaneous adsorption and Langmuir-Blodgett transfer of monolayers from an air/water interface. The effect of the immobilization procedure on the structure of the protein complex has been determined from photochemical activity and optical measurements. The experimental variables which are critical for maintaining the structure and function of the protein in the adsorbed state will be discussed.

  9. Artificial photosynthetic reaction centers coupled to light-harvesting antennas

    NASA Astrophysics Data System (ADS)

    Ghosh, Pulak Kumar; Smirnov, Anatoly Yu.; Nori, Franco

    2011-12-01

    We analyze a theoretical model for energy and electron transfer in an artificial photosynthetic system. The photosystem consists of a molecular triad (i.e., with a donor, a photosensitive unit, and an acceptor) coupled to four accessory light-harvesting-antenna pigments. The resonant energy transfer from the antennas to the artificial reaction center (the molecular triad) is described here by the Förster mechanism. We consider two different kinds of arrangements of the accessory light-harvesting pigments around the reaction center. The first arrangement allows direct excitation transfer to the reaction center from all the surrounding pigments. The second configuration transmits energy via a cascade mechanism along a chain of light-harvesting chromophores, where only one chromophore is connected to the reaction center. We show that the artificial photosynthetic system using the cascade energy transfer absorbs photons in a broader wavelength range and converts their energy into electricity with a higher efficiency than the system based on direct couplings between all the antenna chromophores and the reaction center.

  10. Stochastic discrete event simulation of germinal center reactions

    NASA Astrophysics Data System (ADS)

    Figge, Marc Thilo

    2005-05-01

    We introduce a generic reaction-diffusion model for germinal center reactions and perform numerical simulations within a stochastic discrete event approach. In contrast to the frequently used deterministic continuum approach, each single reaction event is monitored in space and time in order to simulate the correct time evolution of this complex biological system. Germinal centers play an important role in the immune system by performing a reaction that aims at improving the affinity between antibodies and antigens. Our model captures experimentally observed features of this reaction, such as the development of the remarkable germinal center morphology and the maturation of antibody-antigen affinity in the course of time. We model affinity maturation within a simple affinity class picture and study it as a function of the distance between the initial antibody-antigen affinity and the highest possible affinity. The model reveals that this mutation distance may be responsible for the experimentally observed all-or-none behavior of germinal centers; i.e., they generate either mainly output cells of high affinity or no high-affinity output cells at all. Furthermore, the exact simulation of the system dynamics allows us to study the hypothesis of cell recycling in germinal centers as a mechanism for affinity optimization. A comparison of three possible recycling pathways indicates that affinity maturation is optimized by a recycling pathway that has previously not been taken into account in deterministic continuum models.

  11. Evolution of heliobacteria: implications for photosynthetic reaction center complexes

    NASA Technical Reports Server (NTRS)

    Vermaas, W. F.; Blankenship, R. E. (Principal Investigator)

    1994-01-01

    The evolutionary position of the heliobacteria, a group of green photosynthetic bacteria with a photosynthetic apparatus functionally resembling Photosystem I of plants and cyanobacteria, has been investigated with respect to the evolutionary relationship to Gram-positive bacteria and cyanobacteria. On the basis of 16S rRNA sequence analysis, the heliobacteria appear to be most closely related to Gram-positive bacteria, but also an evolutionary link to cyanobacteria is evident. Interestingly, a 46-residue domain including the putative sixth membrane-spanning region of the heliobacterial reaction center protein show rather strong similarity (33% identity and 72% similarity) to a region including the sixth membrane-spanning region of the CP47 protein, a chlorophyll-binding core antenna polypeptide of Photosystem II. The N-terminal half of the heliobacterial reaction center polypeptide shows a moderate sequence similarity (22% identity over 232 residues) with the CP47 protein, which is significantly more than the similarity with the Photosystem I core polypeptides in this region. An evolutionary model for photosynthetic reaction center complexes is discussed, in which an ancestral homodimeric reaction center protein (possibly resembling the heliobacterial reaction center protein) with 11 membrane-spanning regions per polypeptide has diverged to give rise to the core of Photosystem I, Photosystem II, and of the photosynthetic apparatus in green, purple, and heliobacteria.

  12. Artificial photosynthetic reaction centers coupled to light-harvesting antennas.

    PubMed

    Ghosh, Pulak Kumar; Smirnov, Anatoly Yu; Nori, Franco

    2011-12-01

    We analyze a theoretical model for energy and electron transfer in an artificial photosynthetic system. The photosystem consists of a molecular triad (i.e., with a donor, a photosensitive unit, and an acceptor) coupled to four accessory light-harvesting-antenna pigments. The resonant energy transfer from the antennas to the artificial reaction center (the molecular triad) is described here by the Förster mechanism. We consider two different kinds of arrangements of the accessory light-harvesting pigments around the reaction center. The first arrangement allows direct excitation transfer to the reaction center from all the surrounding pigments. The second configuration transmits energy via a cascade mechanism along a chain of light-harvesting chromophores, where only one chromophore is connected to the reaction center. We show that the artificial photosynthetic system using the cascade energy transfer absorbs photons in a broader wavelength range and converts their energy into electricity with a higher efficiency than the system based on direct couplings between all the antenna chromophores and the reaction center.

  13. Nuclear Reaction Data File for Astrophysics (NRDF/A) in Hokkaido University Nuclear Reaction Data Center

    NASA Astrophysics Data System (ADS)

    Katō, Kiyoshi; Kimura, Masaaki; Furutachi, Naoya; Togashi, Tomoaki; Makinaga, Ayano; Otuka, Naohiko

    2010-06-01

    The activities of the Japan Nuclear Reaction Data Centre is explained. The main task of the centre is data compilation of Japanese nuclear reaction data in collaboration of the International Network of Nuclear Reaction Data Centres. As one of recent activities, preparation of a new database (NRDF/A) and evaluation of astronuclear reaction data are reported. Collaboration in the nuclear data activities among Asian countries is proposed.

  14. Light saturation curves show competence of the water splitting complex in inactive Photosystem II reaction centers.

    PubMed

    Nedbal, L; Gibas, C; Whitmarsh, J

    1991-12-01

    Photosystem II complexes of higher plants are structurally and functionally heterogeneous. While the only clearly defined structural difference is that Photosystem II reaction centers are served by two distinct antenna sizes, several types of functional heterogeneity have been demonstrated. Among these is the observation that in dark-adapted leaves of spinach and pea, over 30% of the Photosystem II reaction centers are unable to reduce plastoquinone to plastoquinol at physiologically meaningful rates. Several lines of evidence show that the impaired reaction centers are effectively inactive, because the rate of oxidation of the primary quinone acceptor, QA, is 1000 times slower than in normally active reaction centers. However, there are conflicting opinions and data over whether inactive Photosystem II complexes are capable of oxidizing water in the presence of certain artificial electron acceptors. In the present study we investigated whether inactive Photosystem II complexes have a functional water oxidizing system in spinach thylakoid membranes by measuring the flash yield of water oxidation products as a function of flash intensity. At low flash energies (less that 10% saturation), selected to minimize double turnovers of reaction centers, we found that in the presence of the artificial quinone acceptor, dichlorobenzoquinone (DCBQ), the yield of proton release was enhanced 20±2% over that observed in the presence of dimethylbenzoquinone (DMBQ). We argue that the extra proton release is from the normally inactive Photosystem II reaction centers that have been activated in the presence of DCBQ, demonstrating their capacity to oxidize water in repetitive flashes, as concluded by Graan and Ort (Biochim Biophys Acta (1986) 852: 320-330). The light saturation curves indicate that the effective antenna size of inactive reaction centers is 55±12% the size of active Photosystem II centers. Comparison of the light saturation dependence of steady state oxygen evolution

  15. Electron transfer in native and mutated photosystem I reaction centers

    NASA Astrophysics Data System (ADS)

    Savikhin, Sergei; Xu, Wu; Chitnis, Parag; Struve, Walter

    2002-03-01

    Femtosecond time-resolved absorption difference studies were performed on photosystem I complexes from the cyanobacterium Synechocystis sp. PCC 6803. The overal electron transfer from the special pair P700 to the secondary acceptor A1 has been shown to be 10 ps, twice shorter than the previously estimated value. Similar studies were performed on more than 10 genetically engineered species, where protein structure was altered in the visinity of the reaction center (RC). The functioning of the PS I complex was found to be extremelly sensitive to the protein sequence in the immediate proximity of the RC: less than half of the studied mutations resulted in photosynthetically active complexes, and all of the latter had electron transfer dynamics indistinguishable from that of the wild type. Most of the mutations in the other areas of the PS I, including antenna, did not affect the photosynthetic function of this complex radically. These results confirm the extreme importance of the precise RC structure and demonstrate why millions of years of evolution resulted in only two types of topologically similar RC's shared by all photosynthetic organisms.

  16. Role of Carotenoids in Photosystem II (PSII) Reaction Centers

    NASA Astrophysics Data System (ADS)

    Braslavsky, Silvia E.; Holzwarth, Alfred R.

    2012-11-01

    A photoprotection mechanism operative in closed reaction centers (RCs) is proposed, where-as a consequence of the negative charge on the quinone QA-triplet 3Chl is formed by the radical pair mechanism on the accessory Chl of the normally inactive D2 branch where it can be subsequently quenched by the spatially close β-carotene in the D2 branch. Whereas β-carotene in the D1 branch is more than 17 Å away from the accessory D1-chlorophyll ({Chl_accD_1)} and, therefore, cannot quench the Chl triplet, the D2-carotene is only 13.2 Å away from {Chl_accD_2} . We propose that the D2 branch becomes active in electron transfer and thus plays a photoprotective role when the intact RCs are closed under high photon fluence conditions. This interpretation allows combining many seemingly inconsistent observations in the literature and reveals the so far "elusive" RC triplet quenching mechanism in PSII. Based on laser-induced optoacoustic studies, an important structural role is assigned to the β-carotene in the D1 branch, i.e., this carotene ensures a rigid structure.

  17. Photosynthetic reaction center of green sulfur bacteria studied by EPR

    SciTech Connect

    Nitschke, W.; Rutherford, A.W. ); Fieler, U. )

    1990-04-24

    Membrane preparations of two species of the green sulfur bacteria Chlorobium have been studied be EPR. Three signals were detected which were attributed to iron-sulfur centers acting as electron acceptors in the photosynthetic reaction center. (1) A signal from a center designated F{sub B}, was photoinduced at 4K. (2) A similar signal, F{sub A}, was photoinduced in addition to the F{sub B} signal upon a short period of illumination at 200 K. (3) Further illumination at 200 K resulted in the appearance of a broad feature at g=1.78. This is attributed to the g{sub x} component of an iron-sulfur center designated F{sub X}. The designations of these signals as F{sub B}, F{sub A}, and F{sub X} are based on their spectroscopic similarities to signals in photosystem I (PS I). The orientation dependence of these EPR signals in ordered Chlorobium membrane multilayers is remarkably similar to that of their PS I homologues. A magnetic interaction between the reduced forms of F{sub B} and F{sub A} occurs, which is also very similar to that seen in PS I. The triplet state of P{sub 840}, the primary electron donor, could be photoinduced at 4 K in samples which had been preincubated with sodium dithionite and methyl viologen and then preilluminated at 200 K. The preillumination reduces the iron-sulfur centers while the preincubation is thought to result in the inactivation of an earlier electron acceptor. Orientation studies of the triplet signal in ordered multilayers indicate that the bacteriochlorophylls which act as the primary electron donor in Chlorobium are arranged with a structural geometry almost identical with that of the special pair in purple bacteria. The Chlorobium reaction center appears to be similar in some respects to both PS I and to the purple bacterial reaction center. This is discussed with regard to the evolution of the different types of reaction centers from a common ancestor.

  18. Enthalpy/entropy driven activation of the first interquinone electron transfer in bacterial photosynthetic reaction centers embedded in vesicles of physiologically important phospholipids.

    PubMed

    Milano, Francesco; Dorogi, Márta; Szebényi, Kornélia; Nagy, László; Maróti, Péter; Váró, György; Giotta, Livia; Agostiano, Angela; Trotta, Massimo

    2007-01-01

    The thermodynamics and kinetics of light-induced electron transfer in bacterial photosynthetic RCs are sensitive to physiologically important lipids (phosphatidylcholine, cardiolipin and phosphatidylglycerol) in the environment. The analysis of the temperature-dependence of the rate of the P(+)Q(A)(-)Q(B)-->P(+)Q(A)Q(B)(-) interquinone electron transfer revealed high enthalpy change of activation in zwitterionic or neutral micelles and vesicles and low enthalpy change of activation in vesicles constituted of negatively charged phospholipids. The entropy change of activation was compensated by the changes of enthalpy, thus the free energy change of activation ( approximately 500 meV) did not show large variation in vesicles of different lipids.

  19. Reaction Rate Measurements at the National Criticality Experiments Research Center

    NASA Astrophysics Data System (ADS)

    Bredeweg, T. A.; Bounds, J. A.; Brooks, G. H., Jr.; Favorite, J. A.; Goda, J. M.; Hayes, D. K.; Jackman, K. R.; Little, R. C.; Macinnes, M. R.; Myers, W. L.; Oldham, W. J.; Rundberg, R. S.; Sanchez, R. G.; Schake, A. R.; White, M. C.; Wilkerson, C. W., Jr.

    2014-09-01

    With the resumption of regular operations of the Los Alamos Critical Assemblies at the National Criticality Experiments Research Center (NCERC), located at the Nevada National Security Site, we have embarked upon a series of campaigns to restore the capability to perform integral reaction rate and fission product yield measurements using historical radiochemical methods. This talk will present an overview of the current and future experimental plans, including results from our experimental campaigns on the Comet/Zeus and Flattop assemblies.

  20. Translation of Ligand-Centered Hydrogen Evolution Reaction Activity and Mechanism of a Rhenium-Thiolate from Solution to Modified Electrodes: A Combined Experimental and Density Functional Theory Study.

    PubMed

    Zhang, Wuyu; Haddad, Andrew Z; Garabato, Brady D; Kozlowski, Pawel M; Buchanan, Robert M; Grapperhaus, Craig A

    2017-02-20

    The homogeneous, nonaqueous catalytic activity of the rhenium-thiolate complex ReL3 (L = diphenylphosphinobenzenethiolate) for the hydrogen evolution reaction (HER) has been transferred from nonaqueous homogeneous to aqueous heterogeneous conditions by immobilization on a glassy carbon electrode surface. A series of modified electrodes based on ReL3 and its oxidized precursor [ReL3][PF6] were fabricated by drop-cast methods, yielding catalytically active species with HER overpotentials for a current density of 10 mA/cm(2), ranging from 357 to 919 mV. The overpotential correlates with film resistance as measured by electrochemical impedance spectroscopy and film morphology as determined by scanning and transmission electron microscopy. The lowest overpotential was for films based on the ionic [ReL3][PF6] precursor with the inclusion of carbon black. Stability measurements indicate a 2 to 3 h conditioning period in which the overpotential increases, after which no change in activity is observed within 24 h or upon reimmersion in fresh aqueous, acidic solution. Electronic spectroscopy results are consistent with ReL3 as the active species on the electrode surface; however, the presence of an undetected quantity of catalytically active degradation species cannot be excluded. The HER mechanism was evaluated by Tafel slope analysis, which is consistent with a novel Volmer-Heyrovsky-Tafel-like mechanism that parallels the proposed homogeneous HER pathway. Proposed mechanisms involving traditional metal-hydride processes vs ligand-centered reactivity were examined by density functional theory, including identification and characterization of relevant transition states. The ligand-centered path is energetically favored with protonation of cis-sulfur sites culminating in homolytic S-H bond cleavage with H2 evolution via H atom coupling.

  1. Femtosecond photodichroism studies of isolated photosystem II reaction centers.

    PubMed

    Wiederrecht, G P; Seibert, M; Govindjee; Wasielewski, M R

    1994-09-13

    Photosynthetic conversion of light energy into chemical potential begins in reaction center protein complexes, where rapid charge separation occurs with nearly unit quantum efficiency. Primary charge separation was studied in isolated photosystem II reaction centers from spinach containing 6 chlorophyll a, 2 pheophytin a (Pheo), 1 cytochrome b559, and 2 beta-carotene molecules. Time-resolved pump-probe kinetic spectroscopy was carried out with 105-fs time resolution and with the pump laser polarized parallel, perpendicular, and at the magic angle (54.7 degrees) relative to the polarized probe beam. The time evolution of the transient absorption changes due to the formation of the oxidized primary electron donor P680+ and the reduced primary electron acceptor Pheo- were measured at 820 nm and 545 nm, respectively. In addition, kinetics were obtained at 680 nm, the wavelength ascribed to the Qy transition of the primary electron donor P680 in the reaction center. At each measured probe wavelength the kinetics of the transient absorption changes can be fit to two major kinetic components. The relative amplitudes of these components are strongly dependent on the polarization of the pump beam relative to that of the probe. At the magic angle, where no photoselection occurs, the amplitude of the 3-ps component, which is indicative of the charge separation, dominates. When the primary electron acceptor Pheo is reduced prior to P680 excitation, the 3-ps component is eliminated.

  2. Femtosecond photodischroism studies of isolated photosystem II reaction centers

    SciTech Connect

    Wiederrecht, G.P.; Wasielewski, M.R.; Siebert, M.; Govindjee

    1994-09-13

    Photosynthetic conversion of light energy into chemical potential begins in reaction center protein complexes, where rapid charge separation occurs with nearly unit quantum efficiency. Primary charge separation was studied in isolated photosystem II reaction centers from spinach containing 6 chlorophyll a, 2 pheophytin a (Pheo), 1 cytochrome b{sub 559}, and 2 {beta}-carotene molecules. Time-resolved pump-probe kinetic spectroscopy was carried out with 105-fs time resolution and with the pump laser polarized parallel, perpendicular, and at the magic angle (54.7{degrees}) relative to the polarized probe beam. The time evolution of the oxidized primary electron donor P680{sup +} and the reduced primary electron acceptor Pheo{sup {minus}} were measured at 820 nm and 545 nm, respectively. In addition, kinetics were obtained at 680 nm, the wavelength ascribed to the Q{sub y} transition of the primary electron donor P680 in the reaction center. At each measured probe wavelength the kinetics of the transient absorption changes can be fit to two major kinetic components. The relative amplitudes of these components are strongly dependent on the polarization of the pump beam relative to that of the probe. At the magic angle, where no photoselection occurs, the amplitude of the 3-ps component, which is indicative of the charge separation, dominates. When the primary electron acceptor Pheo is reduced prior to P680 excitation, the 3-ps component is eliminated. 48 refs., 6 figs., 1 tab.

  3. Temperature Dependence of the Rate Constants of Charge Recombination Reactions in Bacterial Reaction Centers

    NASA Astrophysics Data System (ADS)

    Thuy, T. T.; Yen, V. T. H.; Thao, T. T.; Viet, Nguyen Ai

    The bacterial reaction center couples light-induced electron transfer via a tightly bound ubiquinone (QA) to a mobile ubiquinone (QB). Based on the electron transfer theory by Marcus, we have investigated the rate of charge recombination reactions from Rhodopseudomonas viridis and Rhodobacter sphaeroides, by mean of finding an approximation formula. The results obtained are verified for not only at high and low temperature as the previous works but also at the medium temperature range.

  4. A multi-pathway model for photosynthetic reaction center

    NASA Astrophysics Data System (ADS)

    Qin, M.; Shen, H. Z.; Yi, X. X.

    2016-03-01

    Charge separation occurs in a pair of tightly coupled chlorophylls at the heart of photosynthetic reaction centers of both plants and bacteria. Recently it has been shown that quantum coherence can, in principle, enhance the efficiency of a solar cell, working like a quantum heat engine. Here, we propose a biological quantum heat engine (BQHE) motivated by Photosystem II reaction center (PSII RC) to describe the charge separation. Our model mainly considers two charge-separation pathways which is more than that typically considered in the published literature. We explore how these cross-couplings increase the current and power of the charge separation and discuss the effects of multiple pathways in terms of current and power. The robustness of the BQHE against the charge recombination in natural PSII RC and dephasing induced by environments is also explored, and extension from two pathways to multiple pathways is made. These results suggest that noise-induced quantum coherence helps to suppress the influence of acceptor-to-donor charge recombination, and besides, nature-mimicking architectures with engineered multiple pathways for charge separations might be better for artificial solar energy devices considering the influence of environments.

  5. Energy Adventure Center. Activity Book.

    ERIC Educational Resources Information Center

    Carlton, Linda L.

    Energy activities are provided in this student activity book. They include: (1) an energy walk; (2) forms of energy in the home; (3) energy conversion; (4) constructing a solar hot dog cooker (with instructions for drawing a parabola); (5) interviewing senior citizens to learn about energy use in the past; (6) packaging materials; (7) insulation;…

  6. Primary charge separation in isolated photosystem II reaction centers

    SciTech Connect

    Seibert, M.; Toon, S. ); Govindjee ); O'Neil, M.P.; Wasielewski, M.R. )

    1992-08-24

    Primary charge-separation in isolated bacterial reaction center (RC) complex occurs in 2.8 ps at room temperature and 0.7--1.2 ps at 10 K. Because of similarities between the bacterial and photosystem II (PSII) RCs, it has been of considerable interest to obtain analogous charge-separation rates in the higher plant system. Our previous femtosecond transient absorption studies used PSII RC material stabilized with PEG or by exchanging dodecyl maltoside (DM) for Triton in the isolation procedure. These materials gave charge-separation 1/e times of 3.0 [plus minus] 0.6 ps at 4[degree]C and 1.4[plus minus] 0.2 ps at 15 K based on the risetime of transient absorption kinetics at 820 nm. These values were thought to represent the time required for formation of the P680[sup +]-Pheo[sup [minus

  7. Transcriptional analysis of the B cell germinal center reaction

    PubMed Central

    Klein, Ulf; Tu, Yuhai; Stolovitzky, Gustavo A.; Keller, Jeffrey L.; Haddad, Joseph; Miljkovic, Vladan; Cattoretti, Giorgio; Califano, Andrea; Dalla-Favera, Riccardo

    2003-01-01

    The germinal center (GC) reaction is crucial for T cell-dependent immune responses and is targeted by B cell lymphomagenesis. Here we analyzed the transcriptional changes that occur in B cells during GC transit (naïve B cells → centroblasts → centrocytes → memory B cells) by gene expression profiling. Naïve B cells, characterized by the expression of cell cycle-inhibitory and antiapoptotic genes, become centroblasts by inducing an atypical proliferation program lacking c-Myc expression, switching to a proapoptotic program, and down-regulating cytokine, chemokine, and adhesion receptors. The transition from GC to memory cells is characterized by a return to a phenotype similar to that of naïve cells except for an apoptotic program primed for both death and survival and for changes in the expression of cell surface receptors including IL-2 receptor β. These results provide insights into the dynamics of the GC reaction and represent the basis for the analysis of B cell malignancies. PMID:12604779

  8. The Hydrologic Cycle Distributed Active Archive Center

    NASA Technical Reports Server (NTRS)

    Hardin, Danny M.; Goodman, H. Michael

    1995-01-01

    The Marshall Space Flight Center Distributed Active Archive Center in Huntsville, Alabama supports the acquisition, production, archival and dissemination of data relevant to the study of the global hydrologic cycle. This paper describes the Hydrologic Cycle DAAC, surveys its principle data holdings, addresses future growth, and gives information for accessing the data sets.

  9. Structural studies of iron and manganese in photosynthetic reaction centers

    SciTech Connect

    McDermott, A.E.

    1987-11-01

    Electron paramagnetic resonance (EPR) and x-ray absorption spectroscopy (XAS) were used to characterize components involved in the light reactions of photosynthetic reaction centers from spinach and a thermophilic cyanobacterium, Synechococcus sp.: center X, the low electron potential acceptor in Photosystem I (PS I) and the Mn complex involved in water oxidation and oxygen evolution. The dependence of its EPR amplitude on microwave power and temperature indicate an Orbach spin relaxation mechanism involving an excited state at 40 cm/sup -1/. This low energy contributes to its unusually anisotropic g-tensor. XAS of iron in PS I preparations containing ferredoxins A, B and X are consistent with a model with (4Fe-4S) ferredoxins, which are presumably centers A and B and (2Fe-2S) ferredoxins, which would be X. Illumination of dark-adapted Synechococcus PS II samples at 220 to 240 K results in the formation of the multiline EPR signal previously assigned as a Mn S/sub 2/ species, and g = 1.8 and 1.9 signals of Fe/sup 2 +/ Q/sub A//sup -/. In contrast to spinach, illumination at 110 to 160 K produces only a new EPR signal at g = 1.6 which we assign to another configuration of Fe/sup 2+ - Q/sup -/. Following illumination of a S/sub 1/ sample at 140 K or 215 K, the Mn x-ray absorption edge inflection energy changes from 6550 eV to 6551 eV, indicating an oxidation of Mn, and average valences greater than Mn(II). Concomitant changes in the shape of the pre-edge spectrum indicate oxidation of Mn(III) to Mn(IV). The Mn EXAFS spectrum of PS II from Synechococcus is similar in the S/sub 1/ and S/sub 2/ states, indicating O or N ligands at 1.75 +- 0.05 A, transition metal neighbor(s) at 2.75 +- 0.05 A, and N and O ligands at 2.2 A with heterogeneous bond lengths; these data demonstrate the presence of a di-..mu..-oxo bridged Mn structure. 202 refs., 40 figs., 7 tabs.

  10. How to harvest solar energy with the photosynthetic reaction center

    NASA Astrophysics Data System (ADS)

    Balaeff, Alexander; Reyes, Justin

    Photosynthetic reaction center (PRC) is a protein complex that performs a key step in photosynthesis: the electron-hole separation driven by photon absorbtion. The PRC has a great promise for applications in solar energy harvesting and photosensing. Such applications, however, are hampered by the difficulty in extracting the photogenerated electric charge from the PRC. To that end, it was proposed to attach the PRC to a molecular wire through which the charge could be collected. In order to find the attachment point for the wire that would maximize the rate of charge outflow from the PRC, we performed a computational study of the PRC from the R. virdis bacterium. An ensemble of PRC structures generated by a molecular dynamics simulation was used to calculate the rate of charge transport from the site of initial charge separation to several trial sites on the protein surface. The Pathways model was used to calculate the charge transfer rate in each step of the network of heme co-factors through which the charge transport was presumed to proceed. A simple kinetic model was then used to determine the overall rate of the multistep charge transport. The calculations revealed several candidate sites for the molecular wire attachment, recommended for experimental verification.

  11. Primary charge separation in isolated photosystem II reaction centers

    SciTech Connect

    Seibert, M.; Toon, S.; Govindjee; O`Neil, M.P.; Wasielewski, M.R.

    1992-08-24

    Primary charge-separation in isolated bacterial reaction center (RC) complex occurs in 2.8 ps at room temperature and 0.7--1.2 ps at 10 K. Because of similarities between the bacterial and photosystem II (PSII) RCs, it has been of considerable interest to obtain analogous charge-separation rates in the higher plant system. Our previous femtosecond transient absorption studies used PSII RC material stabilized with PEG or by exchanging dodecyl maltoside (DM) for Triton in the isolation procedure. These materials gave charge-separation 1/e times of 3.0 {plus_minus} 0.6 ps at 4{degree}C and 1.4{plus_minus} 0.2 ps at 15 K based on the risetime of transient absorption kinetics at 820 nm. These values were thought to represent the time required for formation of the P680{sup +}-Pheo{sup {minus}} state. Recent results of Hastings et al. obtained at high data acquisition rates and low flash intensities, suggest that the Pheo{sup {minus}} state may form more slowly. In light of this work, we have carried out additional time domain studies of both electron transport and energy transfer phenomena in stabilized DM PSII RCs at room temperature. We used a 1-kHz repetition rate femtosecond transient absorption spectrometer with a 200 fs instrumental time resolution and compared the results with those obtained by others using frequency domain hole-burning techniques.

  12. Photocurrent generation in diamond electrodes modified with reaction centers.

    PubMed

    Caterino, Roberta; Csiki, Réka; Lyuleeva, Alina; Pfisterer, Jonas; Wiesinger, Markus; Janssens, Stoffel D; Haenen, Ken; Cattani-Scholz, Anna; Stutzmann, Martin; Garrido, Jose A

    2015-04-22

    Photoactive reaction centers (RCs) are protein complexes in bacteria able to convert sunlight into other forms of energy with a high quantum yield. The photostimulation of immobilized RCs on inorganic electrodes result in the generation of photocurrent that is of interest for biosolar cell applications. This paper reports on the use of novel electrodes based on functional conductive nanocrystalline diamond onto which bacterial RCs are immobilized. A three-dimensional conductive polymer scaffold grafted to the diamond electrodes enables efficient entrapment of photoreactive proteins. The electron transfer in these functional diamond electrodes is optimized through the use of a ferrocene-based electron mediator, which provides significant advantages such as a rapid electron transfer as well as high generated photocurrent. A detailed discussion of the generated photocurrent as a function of time, bias voltage, and mediators in solution unveils the mechanisms limiting the electron transfer in these functional electrodes. This work featuring diamond-based electrodes in biophotovoltaics offers general guidelines that can serve to improve the performance of similar devices based on different materials and geometries.

  13. Technical activities 1986, Center for Basic Standards

    NASA Astrophysics Data System (ADS)

    Heydemann, P. L. M.

    1986-10-01

    The report summarizes the research and technical activities of the Center for Basic Standards during the Fiscal Year 1986. These activities include work in the areas of electricity, temperature and pressure, mass and length, time and frequency, quantum metrology, and quantum physics.

  14. Procedure for rapid isolation of photosynthetic reaction centers using cytochrome c affinity chromatography

    SciTech Connect

    Brudvig, G.W.; Worland, S.T.; Sauer, K.

    1983-02-01

    Horse heart cytochrome c linked to Sepharose 4B is used to purify reaction centers from Rhodopseudomonas sphaeroides R-26. This procedure allows for an initial recovery of 80-90% of the bacterial reaction centers present in chromatophore membranes. High purity reaction centers (A/sub 280//A/sub 802/ < 1.30) can be obtained with a 30% recovery. Reaction centers from wild-type Rps. sphaeroides and Rps. capsulata also bind to a cytochrome c column. Cytochrome c affinity chromatography can also be used to isolate photosystem I complexes from spinach chloroplasts.

  15. Modification of photosystem I reaction center by the extraction and exchange of chlorophylls and quinones.

    PubMed

    Itoh, S; Iwaki, M; Ikegami, I

    2001-10-30

    The photosystem (PS) I photosynthetic reaction center was modified thorough the selective extraction and exchange of chlorophylls and quinones. Extraction of lyophilized photosystem I complex with diethyl ether depleted more than 90% chlorophyll (Chl) molecules bound to the complex, preserving the photochemical electron transfer activity from the primary electron donor P700 to the acceptor chlorophyll A(0). The treatment extracted all the carotenoids and the secondary acceptor phylloquinone (A(1)), and produced a PS I reaction center that contains nine molecules of Chls including P700 and A(0), and three Fe-S clusters (F(X), F(A) and F(B)). The ether-extracted PS I complex showed fast electron transfer from P700 to A(0) as it is, and to FeS clusters if phylloquinone or an appropriate artificial quinone was reconstituted as A(1). The ether-extracted PS I enabled accurate detection of the primary photoreactions with little disturbance from the absorbance changes of the bulk pigments. The quinone reconstitution created the new reactions between the artificial cofactors and the intrinsic components with altered energy gaps. We review the studies done in the ether-extracted PS I complex including chlorophyll forms of the core moiety of PS I, fluorescence of P700, reaction rate between A(0) and reconstituted A(1), and the fast electron transfer from P700 to A(0). Natural exchange of chlorophyll a to 710-740 nm absorbing chlorophyll d in PS I of the newly found cyanobacteria-like organism Acaryochloris marina was also reviewed. Based on the results of exchange studies in different systems, designs of photosynthetic reaction centers are discussed.

  16. Secondary Activity Category | STORET Legacy Data Center ...

    EPA Pesticide Factsheets

    2007-05-16

    The U.S. Environmental Protection Agency (EPA) maintains two data management systems containing water quality information for the nation's waters: the Legacy Data Center (LDC), and STORET. The LDC is a static, archived database and STORET is an operational system actively being populated with water quality data.

  17. Germinal center reaction: antigen affinity and presentation explain it all.

    PubMed

    Oropallo, Michael A; Cerutti, Andrea

    2014-07-01

    The selection and expansion of B cells undergoing affinity maturation in the germinal center is a hallmark of humoral immunity. A recent paper in Nature provides new insights into the relationships between the affinity of the immunoglobulin receptor for antigen, the ability of B cells to present antigen to T cells, and the processes of selection, mutation, and clonal expansion in the germinal center.

  18. Species differences in unlocking B-side electron transfer in bacterial reaction centers

    DOE PAGES

    Dylla, Nicholas P.; Faries, Kaitlyn M.; Wyllie, Ryan M.; ...

    2016-06-21

    The structure of the bacterial photosynthetic reaction center (RC) reveals symmetry-related electron transfer (ET) pathways, but only one path is used in native RCs. Analogous mutations have been made in two Rhodobacter (R.) species. A glutamic acid at position 133 in the M subunit increases transmembrane charge separation via the naturally inactive (B-side) path through impacts on primary ET in mutant R. sphaeroidesRCs. Prior work showed that the analogous substitution in the R. capsulatusRC also increases B-side activity, but mainly affects secondary ET. Finally, the overall yields of transmembrane ET are similar, but enabled in fundamentally different ways.

  19. RNA polymerase active center: the molecular engine of transcription.

    PubMed

    Nudler, Evgeny

    2009-01-01

    RNA polymerase (RNAP) is a complex molecular machine that governs gene expression and its regulation in all cellular organisms. To accomplish its function of accurately producing a full-length RNA copy of a gene, RNAP performs a plethora of chemical reactions and undergoes multiple conformational changes in response to cellular conditions. At the heart of this machine is the active center, the engine, which is composed of distinct fixed and moving parts that serve as the ultimate acceptor of regulatory signals and as the target of inhibitory drugs. Recent advances in the structural and biochemical characterization of RNAP explain the active center at the atomic level and enable new approaches to understanding the entire transcription mechanism, its exceptional fidelity and control.

  20. Relevance of the photosynthetic reaction center from purple bacteria to the structure of photosystem II

    SciTech Connect

    Michel, H.; Deisenhofer, J.

    1988-01-12

    Photosynthetic organisms are able to oxidize organic or inorganic compounds upon the absorption of light, and they use the extracted electron for the fixation of carbon dioxide. The most important oxidation product is oxygen due to the splitting of water. In eukaryotes these processes occur in photosystem II of chloroplasts. Among prokaryotes photosynthetic oxygen evolution is restricted to cyanobacteria and prochloron-type organisms. How water is split in the oxygen-evolving complex of photosystem II belongs to the most important question to be answered. The primary charge separation occurs in the reaction center of photosystem II. This reaction center is a complex consisting of peripheral and integral membrane proteins, several chlorophyll A molecules, two pheophytin A molecules, two and three plastoquinone molecules, and one non-heme iron atom. The location of the photosystem II reaction center is still a matter of debate. Nakatani et al. (l984) concluded from fluorescence measurements that a protein of apparent molecular weight 47,000 (CP47) is the apoprotein of the photosystem II reaction center. A different view emerged from work with the photosynthetic reaction centers from the purple bacteria. The amino acid sequence of the M subunit of the reaction center from Phodopseudomonas (Rps.) sphaeroides has sequence homologies with the D1 protein from spinach. A substantial amount of structural information can be obtained with the reaction center from Rhodopseudomonas viridis, which can be crystallized. Here the authors discuss the structure of the photosynthetic reaction center from the purple bacterium Rps. viridis and describe the role of those amino acids that are conserved between the bacterial and photosystem II reaction center.

  1. Naval weapons center active fault map series

    NASA Astrophysics Data System (ADS)

    Roquemore, G. R.; Zellmer, J. T.

    1987-08-01

    The NWC Active Fault Map Series shows the locations of active faults and features indicative of active faulting within much of Indian Wells Valley and portions of the Randsburg Wash/Mojave B test range areas of the Naval Weapons Center. Map annotations are used extensively to identify criteria employed in identifying the fault offsets, and to present other valuable data. All of the mapped faults show evidence of having moved during about the last 12,500 years or represent geologically young faults that occur within seismic gaps. Only faults that offset the surface or show other evidence of surface deformation were mapped. A portion of the City of Ridgecrest is recommended as being a Seismic Hazard Special Studies Zone in which detailed earthquake hazard studies should be required.

  2. Oxygen in activator centers of zinc sulfide

    SciTech Connect

    Golobeva, N.P.; Fok, M.V.

    1986-05-01

    The authors observed the sensitized luminescence of Tm and Dy without addition of Cu and Ag in samples which had been obtained by the sulfonation of zinc sulfide in hydrogen sulfide; the zinc sulfide has a copper concentration below 5.10/sup -6/ mass %. In this case the excitation can be transmitted from the ZnS lattice to the rare-earth activators mainly through defects including oxygen. The following conclusions were made. In the case of activated ZnS, oxygen is present in formations accounting for the excitation and luminescence of a number of luminophors. When an activator is introduced in the region of ZnS layer faults, where also the oxygen must be located, the positioning of the faults in close vicinity is facilitated even when the oxygen concentration of the ZnS is low. All this must be considered when models of luminescence centers of zinc sulfide are developed.

  3. Catawba Science Center solar activities. Final report

    SciTech Connect

    1983-01-01

    Two demonstration solar water heaters were built. One was to be used at the Science Center and the other with traveling programs. This was completed and both units are being used for these programs which continue. We were able to build a library of 99 solar energy books and booklets that are available to the public for reference. We also conducted programs for 683 students of all ages. The culminating activity was the planned Energy Awareness Festival. This was held on September 26, 1981 and attracted 450 area citizens. We offered free exhibit space and hosted 17 exhibitors.

  4. [High-order derivative spectroscopy of infrared absorption spectra of the reaction centers from Rhodobacter sphaeroides].

    PubMed

    2005-01-01

    The infrared absorption spectra of reduced and chemically oxidized reaction center preparations from the purple bacterium Rhodobacter sphaeroides were investigated by means of high-order derivative spectroscopy. The model Gaussian band with a maximum at 810 nm and a half-band of 15 nm found in the absorption spectrum of the reduced reaction center preparation is eliminated after the oxidation of photoactive bacteriochlorophyll dimer (P). This band was related to the absorption of the P(+)y excitonic band of P. On the basis of experimental results, it was concluded that the bleaching of the P(+)y absorption band at 810 nm in the oxidized reaction center preparations gives the main contribution to the blue shift of the 800 nm absorption band of Rb. sphaeroides reaction centers.

  5. Protein structure, electron transfer and evolution of prokaryotic photosynthetic reaction centers

    NASA Technical Reports Server (NTRS)

    Blankenship, R. E.

    1994-01-01

    Photosynthetic reaction centers from a variety of organisms have been isolated and characterized. The groups of prokaryotic photosynthetic organisms include the purple bacteria, the filamentous green bacteria, the green sulfur bacteria and the heliobacteria as anoxygenic representatives as well as the cyanobacteria and prochlorophytes as oxygenic representatives. This review focuses on structural and functional comparisons of the various groups of photosynthetic reaction centers and considers possible evolutionary scenarios to explain the diversity of existing photosynthetic organisms.

  6. Kinetic analysis of the thermal stability of the photosynthetic reaction center from Rhodobacter sphaeroides.

    PubMed

    Hughes, Arwel V; Rees, Paul; Heathcote, Peter; Jones, Michael R

    2006-06-01

    The temperature-induced denaturation of the photosynthetic reaction center from Rhodobacter sphaeroides has been studied through the changes that occur in the absorption spectrum of the bound chromophores on heating. At elevated temperatures, the characteristic absorbance bands of the bacteriochlorins bound to the polypeptides within the reaction center are lost, and are replaced by features typical of unbound bacteriochlorophyll and bacteriopheophytin. The kinetics of the spectral changes cannot be explained by a direct conversion from the functional to the denatured form of the protein, and require the presence of at least one intermediate. Possible mechanisms for the transformation via an intermediate are examined using a global analysis of the kinetic data, and the most likely mechanism is shown to involve a reversible transformation between the native state and an off-pathway intermediate, coupled to an irreversible transformation to the denatured state. The activation energies for the transformations between the three components are calculated from the effect of temperature on the individual rate constants, and the likely structural changes of the protein during the temperature-induced transformation are discussed.

  7. High throughput engineering to revitalize a vestigial electron transfer pathway in bacterial photosynthetic reaction centers.

    PubMed

    Faries, Kaitlyn M; Kressel, Lucas L; Wander, Marc J; Holten, Dewey; Laible, Philip D; Kirmaier, Christine; Hanson, Deborah K

    2012-03-09

    Photosynthetic reaction centers convert light energy into chemical energy in a series of transmembrane electron transfer reactions, each with near 100% yield. The structures of reaction centers reveal two symmetry-related branches of cofactors (denoted A and B) that are functionally asymmetric; purple bacterial reaction centers use the A pathway exclusively. Previously, site-specific mutagenesis has yielded reaction centers capable of transmembrane charge separation solely via the B branch cofactors, but the best overall electron transfer yields are still low. In an attempt to better realize the architectural and energetic factors that underlie the directionality and yields of electron transfer, sites within the protein-cofactor complex were targeted in a directed molecular evolution strategy that implements streamlined mutagenesis and high throughput spectroscopic screening. The polycistronic approach enables efficient construction and expression of a large number of variants of a heteroligomeric complex that has two intimately regulated subunits with high sequence similarity, common features of many prokaryotic and eukaryotic transmembrane protein assemblies. The strategy has succeeded in the discovery of several mutant reaction centers with increased efficiency of the B pathway; they carry multiple substitutions that have not been explored or linked using traditional approaches. This work expands our understanding of the structure-function relationships that dictate the efficiency of biological energy-conversion reactions, concepts that will aid the design of bio-inspired assemblies capable of both efficient charge separation and charge stabilization.

  8. Photochemical reactions of metal nitrosyl complexes. Mechanisms of NO reactions with biologically relevant metal centers

    DOE PAGES

    Ford, Peter C.

    2001-01-01

    Tmore » he discoveries that nitric oxide (a.k.a. nitrogen monoxide) serves important roles in mammalian bioregulation and immunology have stimulated intense interest in the chemistry and biochemistry of NO and derivatives such as metal nitrosyl complexes. Also of interest are strategies to deliver NO to biological targets on demand. One such strategy would be to employ a precursor which displays relatively low thermal reactivity but is photochemically active to release NO.his proposition led us to investigate laser flash and continuous photolysis kinetics of nitrosyl complexes such as the Roussin's iron-sulfur-nitrosyl cluster anions Fe 2 S 2 ( NO ) 4 2 − and Fe 4 S 3 ( NO ) 7 − and several ruthenium salen and porphyrin nitrosyls.hese include studies using metal-nitrosyl photochemistry as a vehicle for delivering NO to hypoxic cell cultures in order to sensitize γ -radiation damage. Also studied were the rates and mechanisms of NO “on” reactions with model water soluble heme compounds, the ferriheme protein met-myoglobin and various ruthenium complexes using ns laser flash photolysis techniques. An overview of these studies is presented.« less

  9. Spectroscopic studies of energy transfer in photosynthetic reaction centers of higher plants

    SciTech Connect

    Tabbutt, S.

    1987-09-01

    The focus of this thesis is excitation transfer and primary photochemistry in spinach chloroplasts and sub-chloroplast particles. The fluorescence kinetics are measured with a synchronously pumped, mode-locked dye laser excitation source and a reverse single photon-counting timing detection system. Very little has been reported on the fluorescence properties of photosystem I (PS I) due to its relatively weak emission compared to photosystem II (PS II). Using a PS I complex isolated from spinach, two emission bands, 690 nm and 722 nm were observed. The 690 nm fluorescence kinetics has an instrument limited (25 ps) rise and is best fit to three exponential decay components: slow, 2.2 to 2.5 ns; middle, 250 to 300 ps; and fast, 40 to 100 ps. Both the yield and kinetics are temperature independent (77 to 295K). The 722 nm emission is dramatically temperature dependent. At 295K the fluorescence lifetimes at 720 nm are identical to those at 690 nm. Upon lowering the temperature the lifetimes of all three decay components increase, a measurable risetime (>25 ps) grows in at temperatures below 265K, and the fluorescence intensity at 722 nm increases about 20-fold from 295K to 77K. These studies provide excitation transfer rates and activation energies within the PS I centers. The PS I emission data can be explained by two Chl a species: an antenna pool emitting at 690 nm and the reaction center emitting at 722 nm. The PSI reaction center complex (CP1) fluorescence intensity under continuous actinic illumination (690 nm) decreased by about 20% with the same kinetics as the optical bleaching at 699 nm. The kinetics and magnitudes of the fluorescence decrease and photobleaching depend upon excitation intensity, ascorbate concentration, ferri/ferrocyanide redox titration and phenasinemethosulfate concentration. 168 refs., 38 figs., 4 tabs.

  10. Photosynthetic antennas and reaction centers: Current understanding and prospects for improvement

    SciTech Connect

    Blankenship, R.E.

    1996-09-01

    A brief introduction to the principles, structures and kinetic processes that take place in natural photosynthetic reaction center complexes is presented. Energy is first collected by an antenna system, and is transferred to a reaction center complex where primary electron transfer takes place. Secondary reactions lead to oxidation of water and reduction of CO{sub 2} in some classes of organisms. Antenna systems are highly regulated to maximize energy collection efficiency while avoiding photodamage. Some areas that are presently not well understood are listed.

  11. Pigment organization and their interactions in reaction centers of photosystem II: optical spectroscopy at 6 K of reaction centers with modified pheophytin composition.

    PubMed

    Germano, M; Shkuropatov, A Y; Permentier, H; de Wijn, R; Hoff, A J; Shuvalov, V A; van Gorkom, H J

    2001-09-25

    Photosystem II reaction centers (RC) with selectively exchanged pheophytin (Pheo) molecules as described in [Germano, M., Shkuropatov, A. Ya., Permentier, H., Khatypov, R. A., Shuvalov, V. A., Hoff, A. J., and van Gorkom, H. J. (2000) Photosynth. Res. 64, 189-198] were studied by low-temperature absorption, linear and circular dichroism, and triplet-minus-singlet absorption-difference spectroscopy. The ratio of extinction coefficients epsilon(Pheo)/epsilon(Chl) for Q(Y) absorption in the RC is approximately 0.40 at 6 K and approximately 0.45 at room temperature. The presence of 2 beta-carotenes, one parallel and one perpendicular to the membrane plane, is confirmed. Absorption at 670 nm is due to the perpendicular Q(Y) transitions of the two peripheral chlorophylls (Chl) and not to either Pheo. The "core" pigments, two Pheo and four Chl absorb in the 676-685 nm range. Delocalized excited states as predicted by the "multimer model" are seen in the active branch. The inactive Pheo and the nearby Chl, however, mainly contribute localized transitions at 676 and 680 nm, respectively, although large CD changes indicate that exciton interactions are present on both branches. Replacement of the active Pheo prevents triplet formation, causes an LD increase at 676 and 681 nm, a blue-shift of 680 nm absorbance, and a bleach of the 685 nm exciton band. The triplet state is mainly localized on the Chl corresponding to B(A) in purple bacteria. Both Pheo Q(Y) transitions are oriented out of the membrane plane. Their Q(X) transitions are parallel to that plane, so that the Pheos in PSII are structurally similar to their homologues in purple bacteria.

  12. Is there a conserved interaction between cardiolipin and the type II bacterial reaction center?

    PubMed Central

    Wakeham, M C; Sessions, R B; Jones, M R; Fyfe, P K

    2001-01-01

    In a recent publication, the structural details of an interaction between the Rhodobacter sphaeroides reaction center and the anionic phospholipid diphosphatidyl glycerol (cardiolipin) were described (K. E. McAuley, P. K. Fyfe, J. P. Ridge, N. W. Isaacs, R. J. Cogdell, and M. R. Jones, 1999, Proc. Natl. Acad. Sci. U.S.A. 96:14706-14711). This was the first crystallographic description of an interaction between this biologically important lipid and an integral membrane protein and was also the first piece of evidence that the reaction center has a specific interaction with cardiolipin. We have examined the extent to which the residues that interact with the cardiolipin are conserved in other species of photosynthetic bacteria with this type of reaction center and discuss the possibility that this cardiolipin binding site is a conserved feature of these reaction centers. We look at how sequence variations that would affect the shape of the cardiolipin binding site might affect the protein-cardiolipin interaction, by modeling the binding of cardiolipin to the reaction center from Rhodopseudomonas viridis. PMID:11222300

  13. Lipid binding to the carotenoid binding site in photosynthetic reaction centers.

    PubMed

    Deshmukh, Sasmit S; Tang, Kai; Kálmán, László

    2011-10-12

    Lipid binding to the carotenoid binding site near the inactive bacteriochlorophyll monomer was probed in the reaction centers of carotenoid-less mutant, R-26 from Rhodobacter sphaeroides. Recently, a marked light-induced change of the local dielectric constant in the vicinity of the inactive bacteriochlorophyll monomer was reported in wild type that was attributed to structural changes that ultimately lengthened the lifetime of the charge-separated state by 3 orders of magnitude (Deshmukh, S. S.; Williams, J. C.; Allen, J. P.; Kalman, L. Biochemistry 2011, 50, 340). Here in the R-26 reaction centers, the combination of light-induced structural changes and lipid binding resulted in a 5 orders of magnitude increase in the lifetime of the charge-separated state involving the oxidized dimer and the reduced primary quinone in proteoliposomes. Only saturated phospholipids with fatty acid chains of 12 and 14 carbon atoms long were bound successfully at 8 °C by cooling the reaction center protein slowly from room temperature. In addition to reporting a dramatic increase of the lifetime of the charge-separated state at physiologically relevant temperatures, this study reveals a novel lipid binding site in photosynthetic reaction center. These results shed light on a new potential application of the reaction center in energy storage as a light-driven biocapacitor since the charges separated by ∼30 Å in a low-dielectric medium can be prevented from recombination for hours.

  14. Utilizing the dynamic stark shift as a probe for dielectric relaxation in photosynthetic reaction centers during charge separation.

    PubMed

    Guo, Zhi; Lin, Su; Woodbury, Neal W

    2013-09-26

    In photosynthetic reaction centers, the electric field generated by light-induced charge separation produces electrochromic shifts in the transitions of reaction center pigments. The extent of this Stark shift indirectly reflects the effective field strength at a particular cofactor in the complex. The dynamics of the effective field strength near the two monomeric bacteriochlorophylls (BA and BB) in purple photosynthetic bacterial reaction centers has been explored near physiological temperature by monitoring the time-dependent Stark shift during charge separation (dynamic Stark shift). This dynamic Stark shift was determined through analysis of femtosecond time-resolved absorbance change spectra recorded in wild type reaction centers and in four mutants at position M210. In both wild type and the mutants, the kinetics of the dynamic Stark shift differ from those of electron transfer, though not in the same way. In wild type, the initial electron transfer and the increase in the effective field strength near the active-side monomer bacteriochlorophyll (BA) occur in synchrony, but the two signals diverge on the time scale of electron transfer to the quinone. In contrast, when tyrosine is replaced by aspartic acid at M210, the kinetics of the BA Stark shift and the initial electron transfer differ, but transfer to the quinone coincides with the decay of the Stark shift. This is interpreted in terms of differences in the dynamics of the local dielectric environment between the mutants and the wild type. In wild type, comparison of the Stark shifts associated with BA and BB on the two quasi-symmetric halves of the reaction center structure confirm that the effective dielectric constants near these cofactors are quite different when the reaction center is in the state P(+)QA(-), as previously determined by Steffen et al. at 1.5 K (Steffen, M. A.; et al. Science 1994, 264, 810-816). However, it is not possible to determine from static, low-temperature measurments if the

  15. Time-resolved tryptophan fluorescence in photosynthetic reaction centers from Rhodobacter sphaeroides

    NASA Technical Reports Server (NTRS)

    Godik, V. I.; Blankenship, R. E.; Causgrove, T. P.; Woodbury, N.

    1993-01-01

    Tryptophan fluorescence of reaction centers isolated from Rhodobacter sphaeroides, both stationary and time-resolved, was studied. Fluorescence kinetics were found to fit best a sum of four discrete exponential components. Half of the initial amplitude was due to a component with a lifetime of congruent to 60 ps, belonging to Trp residues, capable of efficient transfer of excitation energy to bacteriochlorophyll molecules of the reaction center. The three other components seem to be emitted by Trp ground-state conformers, unable to participate in such a transfer. Under the influence of intense actinic light, photooxidizing the reaction centers, the yield of stationary fluorescence diminished by congruent to 1.5 times, while the number of the kinetic components and their life times remained practically unchanged. Possible implications of the observed effects for the primary photosynthesis events are considered.

  16. Native FMO-reaction center supercomplex in green sulfur bacteria: an electron microscopy study.

    PubMed

    Bína, David; Gardian, Zdenko; Vácha, František; Litvín, Radek

    2016-04-01

    Chlorobaculum tepidum is a representative of green sulfur bacteria, a group of anoxygenic photoautotrophs that employ chlorosomes as the main light-harvesting structures. Chlorosomes are coupled to a ferredoxin-reducing reaction center by means of the Fenna-Matthews-Olson (FMO) protein. While the biochemical properties and physical functioning of all the individual components of this photosynthetic machinery are quite well understood, the native architecture of the photosynthetic supercomplexes is not. Here we report observations of membrane-bound FMO and the analysis of the respective FMO-reaction center complex. We propose the existence of a supercomplex formed by two reaction centers and four FMO trimers based on the single-particle analysis of the complexes attached to native membrane. Moreover, the structure of the photosynthetic unit comprising the chlorosome with the associated pool of RC-FMO supercomplexes is proposed.

  17. A single residue controls electron transfer gating in photosynthetic reaction centers

    NASA Astrophysics Data System (ADS)

    Shlyk, Oksana; Samish, Ilan; Matěnová, Martina; Dulebo, Alexander; Poláková, Helena; Kaftan, David; Scherz, Avigdor

    2017-03-01

    Interquinone QA‑ → QB electron-transfer (ET) in isolated photosystem II reaction centers (PSII-RC) is protein-gated. The temperature-dependent gating frequency “k” is described by the Eyring equation till levelling off at T ≥ 240 °K. Although central to photosynthesis, the gating mechanism has not been resolved and due to experimental limitations, could not be explored in vivo. Here we mimic the temperature dependency of “k” by enlarging VD1-208, the volume of a single residue at the crossing point of the D1 and D2 PSII-RC subunits in Synechocystis 6803 whole cells. By controlling the interactions of the D1/D2 subunits, VD1-208 (or 1/T) determines the frequency of attaining an ET-active conformation. Decelerated ET, impaired photosynthesis, D1 repair rate and overall cell physiology upon increasing VD1-208 to above 130 Å3, rationalize the >99% conservation of small residues at D1-208 and its homologous motif in non-oxygenic bacteria. The experimental means and resolved mechanism are relevant for numerous transmembrane protein-gated reactions.

  18. A single residue controls electron transfer gating in photosynthetic reaction centers

    PubMed Central

    Shlyk, Oksana; Samish, Ilan; Matěnová, Martina; Dulebo, Alexander; Poláková, Helena; Kaftan, David; Scherz, Avigdor

    2017-01-01

    Interquinone QA− → QB electron-transfer (ET) in isolated photosystem II reaction centers (PSII-RC) is protein-gated. The temperature-dependent gating frequency “k” is described by the Eyring equation till levelling off at T ≥ 240 °K. Although central to photosynthesis, the gating mechanism has not been resolved and due to experimental limitations, could not be explored in vivo. Here we mimic the temperature dependency of “k” by enlarging VD1-208, the volume of a single residue at the crossing point of the D1 and D2 PSII-RC subunits in Synechocystis 6803 whole cells. By controlling the interactions of the D1/D2 subunits, VD1-208 (or 1/T) determines the frequency of attaining an ET-active conformation. Decelerated ET, impaired photosynthesis, D1 repair rate and overall cell physiology upon increasing VD1-208 to above 130 Å3, rationalize the >99% conservation of small residues at D1-208 and its homologous motif in non-oxygenic bacteria. The experimental means and resolved mechanism are relevant for numerous transmembrane protein-gated reactions. PMID:28300167

  19. Using synthetic model systems to understand charge separation and spin dynamics in photosynthetic reaction centers.

    SciTech Connect

    Wasielewski, M. R.

    1998-08-27

    Our current work in modeling reaction center dynamics has resulted in the observation of each major spin-dependent photochemical pathway that is observed in reaction centers. The development of new, simpler model systems has permitted us to probe deeply into the mechanistic issues that drive these dynamics. Based on these results we have returned to biomimetic chlorophyll-based electron donors to mimic these dynamics. Future studies will focus on the details of electronic structure and energetic of both the donor-acceptor molecules and their surrounding environment that dictate the mechanistic pathways and result in efficient photosynthetic charge separation.

  20. Activation Energy of Tantalum-Tungsten Oxide Thermite Reaction

    SciTech Connect

    Cervantes, O; Kuntz, J; Gash, A; Munir, Z

    2010-02-25

    The activation energy of a high melting temperature sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the High Pressure Spark Plasma Sintering (HPSPS) technique to 300 and 400 C to produce pellets with dimensions of 5 mm diameter by 1.5 mm height. A custom built ignition setup was developed to measure ignition temperatures at high heating rates (500-2000 C {center_dot} min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Unlike the 400 C samples, results show that the samples consolidated to 300 C undergo an abrupt change in temperature response prior to ignition. This change in temperature response has been attributed to the crystallization of the amorphous WO{sub 3} in the SG derived Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465-670 C. The activation energy of the SG derived Ta-WO{sup 3} thermite composite consolidated to 300 and 400 C were determined to be 37.787 {+-} 1.58 kJ {center_dot} mol{sup -1} and 57.381 {+-} 2.26 kJ {center_dot} mol{sup -1}, respectively.

  1. Mimicry of the radical pair and triplet states in photosynthetic reaction centers with a synthetic model

    SciTech Connect

    Wasielewski, M.R.; Greenfield, S.R.; Svec, W.A.

    1997-08-01

    Results are presented on a photosynthetic model system that closely mimics the spin dynamics of triplet state formation found in photosynthetic reaction centers. This research will make it possible to design new models to probe the mechanism of the primary events of photosynthesis.

  2. Observation of multiple radical pair states in photosystem 2 reaction centers.

    PubMed

    Booth, P J; Crystall, B; Ahmad, I; Barber, J; Porter, G; Klug, D R

    1991-07-30

    Charge recombination of the primary radical pair in D1/D2 reaction centers from photosystem 2 has been studied by time-resolved fluorescence and absorption spectroscopy. The kinetics of the primary radical pair are multiexponential and exhibit at least two lifetimes of 20 and 52 ns. In addition, a third lifetime of approximately 500 ps also appears to be present. These multiexponential charge-recombination kinetics reflect either different conformational states of D1/D2 reaction centers, with the different conformers exhibiting different radical pair lifetimes, or relaxations in the free energy of the radical pair state. Whichever model is invoked, the free energies of formation of the different radical pair states exhibit a linear temperature dependence from 100 to 220 K, indicating that they are dominated by entropy with negligible enthalpy contributions. These results are in agreement with previous determinations of the thermodynamics that govern primary charge separation in both D1/D2 reaction centers [Booth, P.J., Crystall, B., Giorgi, L. B., Barber, J., Klug, D.R., & Porter, G. (1990) Biochim. Biophys. Acta 1016, 141-152] and reaction centers of purple bacteria [Woodbury, N.W.T., & Parson, W.W. (1984) Biochim. Biophys. Acta 767, 345-361]. It is possible that these observations reflect structural changes that accompanying primary charge separation and assist in stabilization of the radical pair state thus optimizing the efficiency of primary electron transfer.

  3. Native Mass Spectrometry Characterizes the Photosynthetic Reaction Center Complex from the Purple Bacterium Rhodobacter sphaeroides

    NASA Astrophysics Data System (ADS)

    Zhang, Hao; Harrington, Lucas B.; Lu, Yue; Prado, Mindy; Saer, Rafael; Rempel, Don; Blankenship, Robert E.; Gross, Michael L.

    2017-01-01

    Native mass spectrometry (MS) is an emerging approach to study protein complexes in their near-native states and to elucidate their stoichiometry and topology. Here, we report a native MS study of the membrane-embedded reaction center (RC) protein complex from the purple photosynthetic bacterium Rhodobacter sphaeroides. The membrane-embedded RC protein complex is stabilized by detergent micelles in aqueous solution, directly introduced into a mass spectrometer by nano-electrospray (nESI), and freed of detergents and dissociated in the gas phase by collisional activation. As the collision energy is increased, the chlorophyll pigments are gradually released from the RC complex, suggesting that native MS introduces a near-native structure that continues to bind pigments. Two bacteriochlorophyll a pigments remain tightly bound to the RC protein at the highest collision energy. The order of pigment release and their resistance to release by gas-phase activation indicates the strength of pigment interaction in the RC complex. This investigation sets the stage for future native MS studies of membrane-embedded photosynthetic pigment-protein and related complexes.

  4. Protein modifications affecting triplet energy transfer in bacterial photosynthetic reaction centers.

    PubMed Central

    Laible, P D; Chynwat, V; Thurnauer, M C; Schiffer, M; Hanson, D K; Frank, H A

    1998-01-01

    The efficiency of triplet energy transfer from the special pair (P) to the carotenoid (C) in photosynthetic reaction centers (RCs) from a large family of mutant strains has been investigated. The mutants carry substitutions at positions L181 and/or M208 near chlorophyll-based cofactors on the inactive and active sides of the complex, respectively. Light-modulated electron paramagnetic resonance at 10 K, where triplet energy transfer is thermally prohibited, reveals that the mutations do not perturb the electronic distribution of P. At temperatures > or = 70 K, we observe reduced signals from the carotenoid in most of the RCs with L181 substitutions. In particular, triplet transfer efficiency is reduced in all RCs in which a lysine at L181 donates a sixth ligand to the monomeric bacteriochlorophyll B(B). Replacement of the native Tyr at M208 on the active side of the complex with several polar residues increased transfer efficiency. The difference in the efficiencies of transfer in the RCs demonstrates the ability of the protein environment to influence the electronic overlap of the chromophores and thus the thermal barrier for triplet energy transfer. PMID:9591686

  5. Activities of the Center for Space Construction

    NASA Technical Reports Server (NTRS)

    1993-01-01

    The Center for Space Construction (CSC) at the University of Colorado at Boulder is one of eight University Space Engineering Research Centers established by NASA in 1988. The mission of the center is to conduct research into space technology and to directly contribute to space engineering education. The center reports to the Department of Aerospace Engineering Sciences and resides in the College of Engineering and Applied Science. The college has a long and successful track record of cultivating multi-disciplinary research and education programs. The Center for Space Construction is prominent evidence of this record. At the inception of CSC, the center was primarily founded on the need for research on in-space construction of large space systems like space stations and interplanetary space vehicles. The scope of CSC's research has now evolved to include the design and construction of all spacecraft, large and small. Within this broadened scope, our research projects seek to impact the underlying technological basis for such spacecraft as remote sensing satellites, communication satellites, and other special purpose spacecraft, as well as the technological basis for large space platforms. The center's research focuses on three areas: spacecraft structures, spacecraft operations and control, and regolith and surface systems. In the area of spacecraft structures, our current emphasis is on concepts and modeling of deployable structures, analysis of inflatable structures, structural damage detection algorithms, and composite materials for lightweight structures. In the area of spacecraft operations and control, we are continuing our previous efforts in process control of in-orbit structural assembly. In addition, we have begun two new efforts in formal approach to spacecraft flight software systems design and adaptive attitude control systems. In the area of regolith and surface systems, we are continuing the work of characterizing the physical properties of lunar

  6. A Light-Activated Reaction Manifold.

    PubMed

    Hiltebrandt, Kai; Elies, Katharina; D'hooge, Dagmar R; Blinco, James P; Barner-Kowollik, Christopher

    2016-06-08

    We introduce an efficient reaction manifold where the rate of a thermally induced ligation can be controlled by a photonic field via two competing reaction channels. The effectiveness of the reaction manifold is evidenced by following the transformations of macromolecular chain termini via high-resolution mass spectrometry and subsequently by selective block copolymer formation. The light-controlled reaction manifold consists of a so-called o-quinodimethane species, a photocaged diene, that reacts in the presence of light with suitable enes in a Diels-Alder reaction and undergoes a transformation into imines with amines in the absence of light. The chemical selectivity of the manifold is controlled by the amount of ene present in the reaction and can be adjusted from 100% imine formation (0% photo product) to 5% imine formation (95% photo product). The reported light-controlled reaction manifold is highly attractive because a simple external field is used to switch the selectivity of specific reaction channels.

  7. Structure-function studies of the photosynthetic reaction center using herbicides that compete for the quinone binding site

    SciTech Connect

    Bylina, E.J.

    1995-12-31

    Certain classes of herbicides act as competitive inhibitors of the photosynthetic reaction center. Genetic engineering techniques can be used to generate photosynthetic reaction centers which contain altered quinone binding sites. A genetic system for rapidly screening herbicides developed in the photosynthetic bacterium Rhodobacter capsulatus has been used to examine the effect of different s-triazine herbicides on the growth of bacteria containing reaction centers with altered quinone binding sites. Structural insights into herbicide binding have been obtained by determining the level of resistance or sensitivity to structurally related herbicides in these modified reaction centers.

  8. A Client Reaction Analysis: Final Report for the Lifelong Learning Center, Reading, Pa.

    ERIC Educational Resources Information Center

    Toombs, William; Croyle, Guy E., Jr.

    The Lifelong Learning Center at the Reading Public Library conducted a study to determine how the clients perceived various aspects of the center's activities in terms of their needs and expectations. A survey was mailed to 329 clients; the response rate was 51%. Survey questions asked about (1) clients' satisfaction with access conditions, staff…

  9. Telerobotic activities at Johnson Space Center

    NASA Technical Reports Server (NTRS)

    Price, Charles R.

    1989-01-01

    The Johnson Space Center telerobotic efforts span three major thrusts: (1) sustaining and expanding the capability of the Shuttle manipulator; (2) developing and integrating the multiple telerobotic system of the Space Station; and (3) fostering and applying research in all areas of telerobotics technology within the government, private, and academic sectors.

  10. Genetic probes of structure/function relationships in the Q{sub B} binding site of the photosynthetic reaction center

    SciTech Connect

    Hanson, D.K.; Tiede, D.M.; Nance, S.L.; Chang, Chong-Hwan; Schiffer, M.

    1991-06-25

    In photosynthetic reaction centers, a quinone molecule, Q{sub B}, is the terminal acceptor in light-induced electron transfer. The crystal structure of the reaction center implicates the protonatable amiho acid residues L212Glu and L213Asp in the binding of Q{sub B} to the reaction center and in proton transfer to the anionic forms of Q{sub B} generated by electron transfer from Q{sub A}. Here we report the construction of the double mutant L212Ala-L213Ala by site-specific mutagenesis, and the isolation and preliminary biophysical characterization of revertant and suppressor strains that have regained the ability to grow under photosynthetic conditions. Our results show that neither L212Glu nor L213Asp is essential for efficient light-induced electron or proton transfer in Rhodobacter capsulatus and that second-site mutations, located within the QB binding pocket or at a more distant site, can compensate for mutations at L212 and L213. Acquisition of a single negatively charged residue (at position L213, or on the other side of the binding pocket at position L225) or loss of a positively charged residue (at position M231) is sufficient to restore activity to the complex.

  11. Modeling of reversible charge separation in reaction centers of photosynthesis: an incoherent approach.

    PubMed

    Yakovlev, A G; Shuvalov, V A

    2014-02-21

    Primary charge separation in reaction centers (RCs) of bacterial photosynthesis is modeled in this work. An incoherent population dynamics of RCs states is formulated by kinetic equations. It is assumed that charge separation is accompanied by regular motion of the system along additional coordinates. This motion modulates an energetics of the reactions, and this modulation causes femtosecond oscillations in the population of the states. The best qualitative and quantitative accordance with experimental data on native, modified and mutant RCs of Rba. sphaeroides is achieved in the five states model that includes two excited states P(*)905BAHA and P(*)940BAHA and three charge separated states I, P(+)BA(-)HA and P(+)BAHA(-) (P is a primary electron donor, bacteriochlorophyll dimer, BA and HA are electron acceptors, monomeric bacteriochlorophyll and bacteriopheophytin in active A-branch respectively). The excited states emit at 905 and 940 nm and have approximately the same energy and high interaction rate. The intermediate state I is populated earlier than the P(+)BA(-)HA state and has energy close to the energy of the excited states, a high rate of population and depopulation and spectral identity to the BA(-). A sum of the I and P(+)BA(-)HA populations fits the experimental kinetics of the BA(-) absorption band at 1020 nm. The model explains an oscillatory phenomenon in the kinetics of the P(*) stimulated emission and of the BA(-) absorption. In the schemes without the I state, accordance with the experiment is achieved at unreal parameter values or is not achieved at all. A qualitative agreement of the model with the experiment can be achieved at a wide range of parameter values. The nature of the states I and P(*)940BAHA is discussed in terms of partial charge separation between P and BA and inside P respectively.

  12. Adult Basic Learning in an Activity Center: A Demonstration Approach.

    ERIC Educational Resources Information Center

    Metropolitan Adult Education Program, San Jose, CA.

    Escuela Amistad, an activity center in San Jose, California, is now operating at capacity, five months after its origin. Average daily attendance has been 125 adult students, 18-65, most of whom are females of Mexican-American background. Activities and services provided by the center are: instruction in English as a second language, home…

  13. Double Mutation in Photosystem II Reaction Centers and Elevated CO2 Grant Thermotolerance to Mesophilic Cyanobacterium

    PubMed Central

    Dinamarca, Jorge; Shlyk-Kerner, Oksana; Kaftan, David; Goldberg, Eran; Dulebo, Alexander; Gidekel, Manuel; Gutierrez, Ana; Scherz, Avigdor

    2011-01-01

    Photosynthetic biomass production rapidly declines in mesophilic cyanobacteria grown above their physiological temperatures largely due to the imbalance between degradation and repair of the D1 protein subunit of the heat susceptible Photosystem II reaction centers (PSIIRC). Here we show that simultaneous replacement of two conserved residues in the D1 protein of the mesophilic Synechocystis sp. PCC 6803, by the analogue residues present in the thermophilic Thermosynechococcus elongatus, enables photosynthetic growth, extensive biomass production and markedly enhanced stability and repair rate of PSIIRC for seven days even at 43°C but only at elevated CO2 (1%). Under the same conditions, the Synechocystis control strain initially presented very slow growth followed by a decline after 3 days. Change in the thylakoid membrane lipids, namely the saturation of the fatty acids is observed upon incubation for the different strains, but only the double mutant shows a concomitant major change of the enthalpy and entropy for the light activated QA−→QB electron transfer, rendering them similar to those of the thermophilic strain. Following these findings, computational chemistry and protein dynamics simulations we propose that the D1 double mutation increases the folding stability of the PSIIRC at elevated temperatures. This, together with the decreased impairment of D1 protein repair under increased CO2 concentrations result in the observed photothermal tolerance of the photosynthetic machinery in the double mutant PMID:22216094

  14. Cofactor-specific photochemical function resolved by ultrafast spectroscopy in photosynthetic reaction center crystals.

    PubMed

    Huang, Libai; Ponomarenko, Nina; Wiederrecht, Gary P; Tiede, David M

    2012-03-27

    High-resolution mapping of cofactor-specific photochemistry in photosynthetic reaction centers (RCs) from Rhodobacter sphaeroides was achieved by polarization selective ultrafast spectroscopy in single crystals at cryogenic temperature. By exploiting the fixed orientation of cofactors within crystals, we isolated a single transition within the multicofactor manifold, and elucidated the site-specific photochemical functions of the cofactors associated with the symmetry-related active A and inactive B branches. Transient spectra associated with the initial excited states were found to involve a set of cofactors that differ depending upon whether the monomeric bacteriochlorophylls, BChl(A), BChl(B), or the special pair bacteriochlorophyll dimer, P, was chosen for excitation. Proceeding from these initial excited states, characteristic photochemical functions were resolved. Specifically, our measurements provide direct evidence for an alternative charge separation pathway initiated by excitation of BChl(A) that does not involve P*. Conversely, the initial excited state produced by excitation of BChl(B) was found to decay by energy transfer to P. A clear sequential kinetic resolution of BChl(A) and the A-side bacteriopheophytin, BPh(A), in the electron transfer proceeding from P* was achieved. These experiments demonstrate the opportunity to resolve photochemical function of individual cofactors within the multicofactor RC complexes using single crystal spectroscopy.

  15. Naval Weapons Center Active Fault Map Series.

    DTIC Science & Technology

    1987-08-31

    SECURITY CLASSIFICATION OF ’MiS PACE NWC TP 6828 CONTENTS Introduction . . . . . . . . . . . . . . . . . ........... 2 Active Fault Definition ...established along the trace of the Little Take fault zone, within the City of Ridgecrest. ACTIVE FAULT DEFINITION Although it is a commonly used term...34active fault" lacks a pre- cise and universally accepted definition . Most workers, however, accept the following: "Active fault - a fault along

  16. Mixed lateral preference and peritraumatic reactions to the World Trade Center attacks.

    PubMed

    Chemtob, Claude M; Wang, Yanping; Dugan, Kelly L; Abramovitz, Robert; Marmar, Charles

    2006-11-01

    There is evidence that mixed lateral preference is a risk factor for developing more intense posttraumatic stress disorder symptoms. However, no research has examined whether mixed-handed persons experience greater threat of loss of life and physical injury and more intense emotional reactions (terror, helplessness, horror) during peritraumatic exposure. This study compared the intensity of ratings of perceived threat to life and physical injury and emotional reactions among mixed-handed and fully right-handed mothers directly exposed to the World Trade Center attacks. Controlling for exposure, mixed-handed mothers reported more intense ratings, indicating that mixed lateral preference may be associated with greater peritraumatic emotional distress.

  17. Quantum trajectory tests of radical-pair quantum dynamics in CIDNP measurements of photosynthetic reaction centers

    NASA Astrophysics Data System (ADS)

    Tsampourakis, K.; Kominis, I. K.

    2015-11-01

    Chemically induced dynamic nuclear polarization is a ubiquitous phenomenon in photosynthetic reaction centers. The relevant nuclear spin observables are a direct manifestation of the radical-pair mechanism. We here use quantum trajectories to describe the time evolution of radical-pairs, and compare their prediction of nuclear spin observables to the one derived from the radical-pair master equation. While our approach provides a consistent description, we unravel a major inconsistency within the conventional theory, thus challenging the theoretical interpretation of numerous CIDNP experiments sensitive to radical-pair reaction kinetics.

  18. Geometric phase and quantum interference in photosynthetic reaction center: Regulation of electron transfer

    NASA Astrophysics Data System (ADS)

    Sun, Yuming; Su, Yuehua; Dai, Zhenhong; Wang, WeiTian

    2016-10-01

    Photosynthesis is driven by electron transfer in reaction centers in which the functional unit is composed of several simple molecules C2-symmetrically arranged into two branches. In view of quantum mechanism, both branches are possible pathways traversed by the transferred electron. Due to different evolution of spin state along two pathways in transmembrane electric potential (TEP), quantum state of the transferred electron at the bridged site acquires a geometric phase difference dependent on TEP, the most efficient electron transport takes place in a specific range of TEP beyond which electron transfer is dramatically suppressed. What's more, reaction center acts like elaborately designed quantum device preparing polarized spin dependent on TEP for the transferred electron to regulate the reduction potential at bridged site. In brief, electron transfer generates the TEP, reversely, TEP modulates the efficiency of electron transfer. This may be an important approach to maintaining an appreciable pH environment in photosynthesis.

  19. Evolution of reaction center mimics to systems capable of generating solar fuel.

    PubMed

    Sherman, Benjamin D; Vaughn, Michael D; Bergkamp, Jesse J; Gust, Devens; Moore, Ana L; Moore, Thomas A

    2014-05-01

    Capturing and converting solar energy via artificial photosynthesis offers an ideal way to limit society's dependence on fossil fuel and its myriad consequences. The development and study of molecular artificial photosynthetic reactions centers and antenna complexes and the combination of these constructs with catalysts to drive the photochemical production of a fuel helps to build the understanding needed for development of future scalable technologies. This review focuses on the study of molecular complexes, design of which is inspired by the components of natural photosynthesis, and covers research from early triad reaction centers developed by the group of Gust, Moore, and Moore to recent photoelectrochemical systems capable of using light to convert water to oxygen and hydrogen.

  20. [On the electron stabilization within the quinone acceptor part of Rhodobacter sphaeroides photosynthetic reaction centers].

    PubMed

    Noks, P P; Krasil'nikov, P M; Mamonov, P A; Seĭfullina, N Kh; Uchoa, A F; Baptista, M S

    2008-01-01

    The time evolution of the photoinduced differential absorption spectrum of isolated Rhodobacter sphaeroides photosynthetic reaction centers was investigated. The measurements were carried out in the spectral region of 400-500 nm on the time scale of up to 200 microseconds. The spectral changes observed can be interpreted in terms of the effects of proton shift along hydrogen bonds between the primary quinone acceptor and the protein. A theoretical analysis of the spectrum time evolution was performed, which is based on the consideration of the kinetics of proton tunneling along the hydrogen bond. It was shown that the stabilization of the primary quinone electronic state occurs within the first several tens of microseconds after quinone reduction. It slows down upon the deuteration of reaction centers as well as after adding 90% of glycerol; on the other hand, it accelerates as temperature rises up to 40 degrees C.

  1. Dynamical theory of primary processes of charge separation in the photosynthetic reaction center.

    PubMed

    Lakhno, Victor D

    2005-05-01

    A dynamical theory has been developed for primary separation of charges in the course of photosynthesis. The theory deals with both hopping and superexchange transfer mechanisms. Dynamics of electron transfer from dimeric bacteriochlorophyll to quinone has been calculated. The results obtained agree with experimental data and provide a unified explanation of both the hierarchy of the transfer time in the photosynthetic reaction center and the phenomenon of coherent oscillations accompanying the transfer process.

  2. Isolation and characterization of photosynthetic reaction centers from Rhodopseudomonas capsulata and Rhodopseudomonas sphaeroides

    SciTech Connect

    Worland, S.T.

    1984-09-01

    Reaction centers were isolated by affinity chromatography on equine cytochrome C. Peripheral proteins were removed with 0.05% LDAO. Absorption and EPR spectra and bleaching assays indicate that the reaction centers retained their electron donors and acceptors in the native environment. Three reaction center polypeptides were isolated and submitted for amino-terminal sequence determination. By comparing these sequences to those deduced from DNA, it was established that the M and L subunits are post-translationally modified to remove the aminoterminal Met, whereas the H subunit is not. Inhibition of O/sub 2/ evolution in photosystem II particles from spinach by naphthoquinone derivatives show O/sub 2/ inhibition by bromomethyl and acetoxymethyl derivatives but not with hydroxymethyl derivatives. Inhibition by acetoxymethyl derivatives in irreversible and dependent on illumination suggesting that reduction of the quinone is necessary. Therefore acetoxymethyl derivatives may be useful as suicide reagents for labelling quinone binding sites. Procedures were developed to extract one or both of the quinones present in reaction centers and preserve the integrity of the co-factor binding sites. The H and M subunits were cleaned using furmic acid. Both fragments were isolated from the H subunit, while the larger fragment was isolated from the M subunit. Electrophoretic mobilities of the isolated fragments agrees well with the expected molecular weights. The L subunit was digested with Staphylococcus areus vs protease. The pattern obtained was consistant with the potential sites of cleavage, but it was not possible to assign cleavage sites unambiguously. 112 references, 37 figures, 2 tables.

  3. Marshall Space Flight Center ECLSS technology activities

    NASA Technical Reports Server (NTRS)

    Wieland, Paul

    1990-01-01

    Viewgraphs on Environmental Control and Life Support System (ECLSS) technology activities are presented. Topics covered include: analytical development; ECLSS modeling approach; example of water reclamation modeling needs; and hardware development and testing.

  4. CFD Modeling Activities at the NASA Stennis Space Center

    NASA Technical Reports Server (NTRS)

    Allgood, Daniel

    2007-01-01

    A viewgraph presentation on NASA Stennis Space Center's Computational Fluid Dynamics (CFD) Modeling activities is shown. The topics include: 1) Overview of NASA Stennis Space Center; 2) Role of Computational Modeling at NASA-SSC; 3) Computational Modeling Tools and Resources; and 4) CFD Modeling Applications.

  5. Synthetic Antenna Functioning As Light Harvester in the Whole Visible Region for Enhanced Hybrid Photosynthetic Reaction Centers.

    PubMed

    Hassan Omar, Omar; la Gatta, Simona; Tangorra, Rocco Roberto; Milano, Francesco; Ragni, Roberta; Operamolla, Alessandra; Argazzi, Roberto; Chiorboli, Claudio; Agostiano, Angela; Trotta, Massimo; Farinola, Gianluca M

    2016-07-20

    The photosynthetic reaction center (RC) from the Rhodobacter sphaeroides bacterium has been covalently bioconjugated with a NIR-emitting fluorophore (AE800) whose synthesis was specifically tailored to act as artificial antenna harvesting light in the entire visible region. AE800 has a broad absorption spectrum with peaks centered in the absorption gaps of the RC and its emission overlaps the most intense RC absorption bands, ensuring a consistent increase of the protein optical cross section. The covalent hybrid AE800-RC is stable and fully functional. The energy collected by the artificial antenna is transferred to the protein via FRET mechanism, and the hybrid system outperforms by a noteworthy 30% the overall photochemical activity of the native protein under the entire range of visible light. This improvement in the optical characteristic of the photoenzyme demonstrates the effectiveness of the bioconjugation approach as a suitable route to new biohybrid materials for energy conversion, photocatalysis, and biosensing.

  6. NASA Glenn Research Center Battery Activities Overview

    NASA Technical Reports Server (NTRS)

    Manzo, Michelle A.

    2009-01-01

    This paper will provide an overview of the planned energy storage systems for the Orion Spacecraft and the Aries rockets that will be used in the return journey to the Moon and GRC's involvement in their development. Technology development goals and approaches to provide batteries and fuel cells for the Altair Lunar Lander, the new space suit under development for extravehicular activities (EVA) on the Lunar surface, and the Lunar Surface Systems operations will also be discussed.

  7. Mimicking the germinal center reaction in hybridoma cells to isolate temperature-selective anti-PEG antibodies

    PubMed Central

    Su, Yu-Cheng; Al-Qaisi, Talal S; Tung, Hsin-Yi; Cheng, Tian-Lu; Chuang, Kuo-Hsiang; Chen, Bing-Mae; Roffler, Steve R

    2014-01-01

    Modification of antibody class and binding properties typically requires cloning of antibody genes, antibody library construction, phage or yeast display and recombinant antibody expression. Here, we describe an alternative “cloning-free” approach to generate antibodies with altered antigen-binding and heavy chain isotype by mimicking the germinal center reaction in antibody-secreting hybridoma cells. This was accomplished by lentiviral transduction and controllable expression of activation-induced cytidine deaminase (AID) to generate somatic hypermutation and class switch recombination in antibody genes coupled with high-throughput fluorescence-activated cell sorting (FACS) of hybridoma cells to detect altered antibody binding properties. Starting from a single established hybridoma clone, we isolated mutated antibodies that bind to a low-temperature structure of polyethylene glycol (PEG), a polymer widely used in nanotechnology, biotechnology and pharmaceuticals. FACS of AID-infected hybridoma cells also facilitated rapid identification of class switched variants of monoclonal IgM to monoclonal IgG. Mimicking the germinal center reaction in hybridoma cells may offer a general method to identify and isolate antibodies with altered binding properties and class-switched heavy chains without the need to carry out DNA library construction, antibody engineering and recombinant protein expression. PMID:24874693

  8. Mimicking the germinal center reaction in hybridoma cells to isolate temperature-selective anti-PEG antibodies.

    PubMed

    Su, Yu-Cheng; Al-Qaisi, Talal S; Tung, Hsin-Yi; Cheng, Tian-Lu; Chuang, Kuo-Hsiang; Chen, Bing-Mae; Roffler, Steve R

    2014-01-01

    Modification of antibody class and binding properties typically requires cloning of antibody genes, antibody library construction, phage or yeast display and recombinant antibody expression. Here, we describe an alternative "cloning-free" approach to generate antibodies with altered antigen-binding and heavy chain isotype by mimicking the germinal center reaction in antibody-secreting hybridoma cells. This was accomplished by lentiviral transduction and controllable expression of activation-induced cytidine deaminase (AID) to generate somatic hypermutation and class switch recombination in antibody genes coupled with high-throughput fluorescence-activated cell sorting (FACS) of hybridoma cells to detect altered antibody binding properties. Starting from a single established hybridoma clone, we isolated mutated antibodies that bind to a low-temperature structure of polyethylene glycol (PEG), a polymer widely used in nanotechnology, biotechnology and pharmaceuticals. FACS of AID-infected hybridoma cells also facilitated rapid identification of class switched variants of monoclonal IgM to monoclonal IgG. Mimicking the germinal center reaction in hybridoma cells may offer a general method to identify and isolate antibodies with altered binding properties and class-switched heavy chains without the need to carry out DNA library construction, antibody engineering and recombinant protein expression.

  9. Synthesis and Photophysical Characterization of an Artificial Photosynthetic Reaction Center Exhibiting Acid-Responsive Regulation of Charge Separation

    NASA Astrophysics Data System (ADS)

    Pahk, Ian

    Non-photochemical quenching (NPQ) is a photoprotective regulatory mechanism essential to the robustness of the photosynthetic apparatus of green plants. Energy flow within the low-light adapted reaction centers is dynamically optimized to match the continuously fluctuating light conditions found in nature. Activated by compartmentalized decreases in pH resulting from photosynthetic activity during periods of elevated photon flux, NPQ induces rapid thermal dissipation of excess excitation energy that would otherwise overwhelm the apparatus's ability to consume it. Consequently, the frequency of charge separation decreases and the formation of potentially deleterious, high-energy intermediates slows, thereby reducing the threat of photodamage by disallowing their accumulation. Herein is described the synthesis and photophysical analysis of a molecular triad that mimics the effects of NPQ on charge separation within the photosynthetic reaction centers. Steady-state absorption and emission, time-resolved fluorescence, and transient absorption spectroscopies were used to demonstrate reversible quenching of the first singlet excited state affecting the quantum yield of charge separation by approximately one order of magnitude. As in the natural system, the populations of unquenched and quenched states and, therefore, the overall yields of charge separation were found to be dependent upon acid concentration.

  10. "JCE" Classroom Activity #111: Redox Reactions in Three Representations

    ERIC Educational Resources Information Center

    Nieves, Edgardo L. Ortiz; Barreto, Reizelie; Medina, Zuleika

    2012-01-01

    This activity introduces students to the concept of reduction-oxidation (redox) reactions. To help students obtain a thorough understanding of redox reactions, the concept is explored at three levels: macroscopic, submicroscopic, and symbolic. In this activity, students perform hands-on investigations of the three levels as they work at different…

  11. Energy dissipation in photosynthesis: does the quenching of chlorophyll fluorescence originate from antenna complexes of photosystem II or from the reaction center?

    PubMed

    Bukhov, N G; Heber, U; Wiese, C; Shuvalov, V A

    2001-04-01

    Dissipation of light energy was studied in the moss Rhytidiadelphus squarrosus (Hedw.) Warnst., and in leaves of Spinacia oleracea L. and Arabidopsis thaliana (L.) Heynh., using chlorophyll fluorescence as an indicator reaction. Maximum chlorophyll fluorescence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU)-treated spinach leaves, as produced by saturating light and studied between and -20 degrees C, revealed an activation energy delta E of 0.11 eV. As this suggested recombination fluorescence produced by charge recombination between the oxidized primary donor of photosystem II and reduced pheophytin, a mathematical model explaining fluorescence, and based in part on known characteristics of primary electron-transport reactions, was developed. The model permitted analysis of different modes of fluorescence quenching, two localized in the reaction center of photosystem II and one in the light-harvesting system of the antenna complexes. It predicted differences in the relationship between quenching of variable fluorescence Fv and quenching of basal, so-called F0 fluorescence depending on whether quenching originated from antenna complexes or from reaction centers. Such differences were found experimentally, suggesting antenna quenching as the predominant mechanism of dissipation of light energy in the moss Rhytidiadelphus, whereas reaction-center quenching appeared to be important in spinach and Arabidopsis. Both reaction-center and antenna quenching required activation by thylakoid protonation but only antenna quenching depended on or was strongly enhanced by zeaxanthin. De-protonation permitted relaxation of this quenching with half-times below 1 min. More slowly reversible quenching, tentatively identified as so-called qI or photoinhibitory quenching, required protonation but persisted for prolonged times after de-protonation. It appeared to originate in reaction centers.

  12. Structural analysis of the homodimeric reaction center complex from the photosynthetic green sulfur bacterium Chlorobaculum tepidum.

    PubMed

    He, Guannan; Zhang, Hao; King, Jeremy D; Blankenship, Robert E

    2014-08-05

    The reaction center (RC) complex of the green sulfur bacterium Chlorobaculum tepidum is composed of the Fenna-Matthews-Olson antenna protein (FMO) and the reaction center core (RCC) complex. The RCC complex has four subunits: PscA, PscB, PscC, and PscD. We studied the FMO/RCC complex by chemically cross-linking the purified sample followed by biochemical and spectroscopic analysis. Blue-native gels showed that there were two types of FMO/RCC complexes, which are consistent with complexes with one copy of FMO per RCC and two copies of FMO per RCC. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis analysis of the samples after cross-linking showed that all five subunits of the RC can be linked by three different cross-linkers: bissulfosuccinimidyl suberate, disuccinimidyl suberate, and 3,3-dithiobis-sulfosuccinimidyl propionate. The interaction sites of the cross-linked complex were also studied using liquid chromatography coupled to tandem mass spectrometry. The results indicated that FMO, PscB, PscD, and part of PscA are exposed on the cytoplasmic side of the membrane. PscD helps stabilize FMO to the reaction center and may facilitate transfer of the electron from the RC to ferredoxin. The soluble domain of the heme-containing cytochrome subunit PscC and part of the core subunit PscA are located on the periplasmic side of the membrane. There is a close relationship between the periplasmic portions of PscA and PscC, which is needed for the efficient transfer of the electron between PscC and P840.

  13. Weak temperature dependence of P (+) H A (-) recombination in mutant Rhodobacter sphaeroides reaction centers.

    PubMed

    Gibasiewicz, Krzysztof; Białek, Rafał; Pajzderska, Maria; Karolczak, Jerzy; Burdziński, Gotard; Jones, Michael R; Brettel, Klaus

    2016-06-01

    In contrast with findings on the wild-type Rhodobacter sphaeroides reaction center, biexponential P (+) H A (-)  → PH A charge recombination is shown to be weakly dependent on temperature between 78 and 298 K in three variants with single amino acids exchanged in the vicinity of primary electron acceptors. These mutated reaction centers have diverse overall kinetics of charge recombination, spanning an average lifetime from ~2 to ~20 ns. Despite these differences a protein relaxation model applied previously to wild-type reaction centers was successfully used to relate the observed kinetics to the temporal evolution of the free energy level of the state P (+) H A (-) relative to P (+) B A (-) . We conclude that the observed variety in the kinetics of charge recombination, together with their weak temperature dependence, is caused by a combination of factors that are each affected to a different extent by the point mutations in a particular mutant complex. These are as follows: (1) the initial free energy gap between the states P (+) B A (-) and P (+) H A (-) , (2) the intrinsic rate of P (+) B A (-)  → PB A charge recombination, and (3) the rate of protein relaxation in response to the appearance of the charge separated states. In the case of a mutant which displays rapid P (+) H A (-) recombination (ELL), most of this recombination occurs in an unrelaxed protein in which P (+) B A (-) and P (+) H A (-) are almost isoenergetic. In contrast, in a mutant in which P (+) H A (-) recombination is relatively slow (GML), most of the recombination occurs in a relaxed protein in which P (+) H A (-) is much lower in energy than P (+) H A (-) . The weak temperature dependence in the ELL reaction center and a YLH mutant was modeled in two ways: (1) by assuming that the initial P (+) B A (-) and P (+) H A (-) states in an unrelaxed protein are isoenergetic, whereas the final free energy gap between these states following the protein relaxation is large (~250 meV or

  14. Identification, isolation, and sequence of the reaction center protein genes of the photosynthetic purple bacterium Rhodopseudomonas capsulata

    SciTech Connect

    Hearst, J.E.

    1984-07-01

    Reaction centers in photosynthetic membranes are the centers to which electronic excitation due to light absorption is transferred. This excitation brings about a charge separation between a bacteriochlorophyll molecule and two quinone molecules which ultimately leads to the formation of a hydroquinone. The reduced hydroquinone is then utilized to produce a proton gradient across the membrane and ultimately to produce ATP. We have focused our interest on the structure of the reaction center in the photosynthetic purple bacterium, Rhodopseudomonas capsulata, with the intention of establishing a detailed understanding of these first chemical steps in the natural fixation of sunlight. The methods used to identify and isolate the genes for the three reaction center subunits, L, M, and H, in Rps. capsulata are outlined. These genes have then been sequenced, and the sequences analyzed in detail for their similarity with sequences of comparable proteins from more advanced photosynthetic bacteria such as Anabena, from algae such as Euglena and Chlamydomonas, and from higher plants such as amaranthus, soybean, tobacco and spinach. Homology was found which has been tentatively interpreted to be in the region of quinone binding in all of these reaction centers. There is growing optimism that there will be substantial structural similarity between the reaction centers of the purple bacteria and those of photosystem II in higher plants. This conclusion is important because the x-ray crystal structures of several of the purple bacteria reaction center complexes are presently being worked on and will ultimately be solved.

  15. Phenomenological description of a three-center insertion reaction: an information-theoretic study.

    PubMed

    Esquivel, Rodolfo O; Flores-Gallegos, Nelson; Dehesa, Jesús S; Angulo, Juan Carlos; Antolín, Juan; López-Rosa, Sheila; Sen, K D

    2010-02-04

    Information-theoretic measures are employed to describe the course of a three-center chemical reaction in terms of detecting the transition state and the stationary points unfolding the bond-forming and bond-breaking regions which are not revealed in the energy profile. The information entropy profiles for the selected reactions are generated by following the intrinsic-reaction-coordinate (IRC) path calculated at the MP2 level of theory from which Shannon entropies in position and momentum spaces at the QCISD(T)/6-311++G(3df,2p) level are determined. Several complementary reactivity descriptors are also determined, such as the dipole moment, the molecular electrostatic potential (MEP) obtained through a multipole expansion (DMA), the atomic charges and electric potentials fitted to the MEP, the hardness and softness DFT descriptors, and several geometrical parameters which support the information-theoretic analysis. New density-based structures related to the bond-forming and bond-breaking regions are proposed. Our results support the concept of a continuum of transient of Zewail and Polanyi for the transition state rather than a single state, which is also in agreement with reaction-force analyses.

  16. Child Care Center Characteristics Associated With Preschoolers’ Physical Activity

    PubMed Central

    Copeland, Kristen A.; Khoury, Jane C.; Kalkwarf, Heidi J.

    2015-01-01

    Introduction Despite children spending long hours in child care centers, it is unknown what center characteristics are associated with children’s moderate to vigorous physical activity (MVPA) at the center and over the 24-hour day. Methods Mixed model ANOVA evaluated associations between 23 center characteristics (e.g., policies, facilities, practices, and staff training) and time in MVPA, measured with accelerometers, at the child care center and over the 24-hour day among 388 preschoolers from 30 randomly selected child care centers in Cincinnati, Ohio. Data collection occurred from November 2009 through January 2011; data analyses occurred in 2012–2014. Results Ninety percent of centers reported scheduling two or more outdoor sessions daily, yet only 40% of children had two or more outdoor sessions; 32% had no time outdoors. Eighty-three percent of centers reported scheduling ≥60 minutes outdoors; 28% of children experienced this during observation. Children spent a mean (SE) of 2.0 (0.06) minutes/hour in MVPA. Children with ≥60 minutes outdoor time had 0.6 minutes/hour more MVPA in child care (p=0.001), and 0.5 minutes/hour over the 24-hour day (p=0.001) than those who did not. Presence of an indoor play space, large outdoor playground, portable or fixed play equipment, staff PA training, weather and clothing policies, and TV/computer use were not related to children’s MVPA. Conclusions Outdoor time occurred less frequently than scheduled. Children with ≥60 minutes of outdoor time at the center were more active than children without. Centers may increase preschoolers’ PA by adhering to the scheduled ≥60 minutes of outdoor time daily. PMID:26585052

  17. Workjobs: Activity-Centered Learning for Early Childhood Education.

    ERIC Educational Resources Information Center

    Lorton, Mary Baratta

    Based on the idea that through active involvement with the materials the child would draw out the generalizations within the material, a teacher's method of activity-centered learning for early childhood education is presented. The first section of the book deals with the development of language through workjobs, emphasizing perception, matching,…

  18. Idaho Senior Center Activities, Activity Participation Level, and Managers' Perceptions of Activity Success.

    ERIC Educational Resources Information Center

    Girvan, James T.; Harris, Frances

    A survey completed by managers of 77 senior centers in Idaho revealed that meals, blood pressure screening, and games and trips were the most successful activities offered. Alzheimer's support groups, library books for loan, and exercise classes were the least successful. Possible reasons for the success or failure of these activities were…

  19. Model for primary electron transfer and coupling of electronic states at reaction centers of purple bacteria

    NASA Astrophysics Data System (ADS)

    Pavlovich, V. S.

    2006-05-01

    A detailed derivation is presented for relations making it possible to describe the effect of temperature on the halfwidth of the P960 and P870 absorption bands and also on the electron transfer (ET) rate at reaction centers (RCs) of the purple bacteria Rps. viridis and Rb. sphaeroides. Primary electron transfer is considered as a resonant nonradiative transition between P* and P+B L - states (where P is a special pair, BL is an additional bacteriochlorophyll in the L branch of the reaction center). It has been shown that the vibrational hα mode with frequency 130 150 cm-1 controls primary electron transfer. It has been found that the matrix element of the electronic transition between the states P* and P+B L - is equal to 12.7 ± 0.9 and 12.0 ± 1.2 cm-1 for Rps. viridis and Rb. sphaeroides respectively. The mechanism is discussed for electron transport from P* and BL and then to bacteriopheophytin HL.

  20. Engineered Photosystem II reaction centers optimize photochemistry versus photoprotection at different solar intensities.

    PubMed

    Vinyard, David J; Gimpel, Javier; Ananyev, Gennady M; Mayfield, Stephen P; Dismukes, G Charles

    2014-03-12

    The D1 protein of Photosystem II (PSII) provides most of the ligating amino acid residues for the Mn4CaO5 water-oxidizing complex (WOC) and half of the reaction center cofactors, and it is present as two isoforms in the cyanobacterium Synechococcus elongatus PCC 7942. These isoforms, D1:1 and D1:2, confer functional advantages for photosynthetic growth at low and high light intensities, respectively. D1:1, D1:2, and seven point mutations in the D1:2 background that are native to D1:1 were expressed in the green alga Chlamydomonas reinhardtii. We used these nine strains to show that those strains that confer a higher yield of PSII charge separation under light-limiting conditions (where charge recombination is significant) have less efficient photochemical turnover, measured in terms of both a lower WOC turnover probability and a longer WOC cycle period. Conversely, these same strains under light saturation (where charge recombination does not compete) confer a correspondingly faster O2 evolution rate and greater protection against photoinhibition. Taken together, the data clearly establish that PSII primary charge separation is a trade-off between photochemical productivity (water oxidation and plastoquinone reduction) and charge recombination (photoprotection). These trade-offs add up to a significant growth advantage for the two natural isoforms. These insights provide fundamental design principles for engineering of PSII reaction centers with optimal photochemical efficiencies for growth at low versus high light intensities.

  1. Isolated Photosystem I Reaction Centers on a Functionalized Gated High Electron Mobility Transistor

    SciTech Connect

    Eliza, Sazia A.; Lee, Ida; Tulip, Fahmida S; Islam, Syed K; Mostafa, Salwa; Greenbaum, Elias; Ericson, Milton Nance

    2011-01-01

    In oxygenic plants, photons are captured with high quantum efficiency by two specialized reaction centers (RC) called Photosystem I (PS I) and Photosystem II (PS II). The captured photon triggers rapid charge separation and the photon energy is converted into an electrostatic potential across the nanometer-scale nm reaction centers. The exogenous photovoltages from a single PS I RC have been previously measured using the technique of Kelvin force probe microscopy (KFM). However, biomolecular photovoltaic applications require two-terminal devices. This paper presents for the first time, a micro-device for detection and characterization of isolated PS I RCs. The device is based on an AlGaN/GaN high electron mobility transistor (HEMT) structure. AlGaN/GaN HEMTs show high current throughputs and greater sensitivity to surface charges compared to other field-effect devices. PS I complexes immobilized on the floating gate of AlGaN/GaN HEMTs resulted in significant changes in the device characteristics under illumination. An analytical model has been developed to estimate the RCs of a major orientation on the functionalized gate surface of the HEMTs.

  2. Functional type 2 photosynthetic reaction centers found in the rare bacterial phylum Gemmatimonadetes

    PubMed Central

    Zeng, Yonghui; Feng, Fuying; Medová, Hana; Dean, Jason; Koblížek, Michal

    2014-01-01

    Photosynthetic bacteria emerged on Earth more than 3 Gyr ago. To date, despite a long evolutionary history, species containing (bacterio)chlorophyll-based reaction centers have been reported in only 6 out of more than 30 formally described bacterial phyla: Cyanobacteria, Proteobacteria, Chlorobi, Chloroflexi, Firmicutes, and Acidobacteria. Here we describe a bacteriochlorophyll a-producing isolate AP64 that belongs to the poorly characterized phylum Gemmatimonadetes. This red-pigmented semiaerobic strain was isolated from a freshwater lake in the western Gobi Desert. It contains fully functional type 2 (pheophytin-quinone) photosynthetic reaction centers but does not assimilate inorganic carbon, suggesting that it performs a photoheterotrophic lifestyle. Full genome sequencing revealed the presence of a 42.3-kb–long photosynthesis gene cluster (PGC) in its genome. The organization and phylogeny of its photosynthesis genes suggests an ancient acquisition of PGC via horizontal transfer from purple phototrophic bacteria. The data presented here document that Gemmatimonadetes is the seventh bacterial phylum containing (bacterio)chlorophyll-based phototrophic species. To our knowledge, these data provide the first evidence that (bacterio)chlorophyll-based phototrophy can be transferred between distant bacterial phyla, providing new insights into the evolution of bacterial photosynthesis. PMID:24821787

  3. Modulating the Redox Potential of the Stable Electron Acceptor, QB, in Mutagenized Photosystem II Reaction Centers.

    SciTech Connect

    Perrine, Zoee; Sayre, Richard

    2011-02-10

    One of the unique features of electron transfer processes in photosystem II (PSII) reaction centers (RC) is the exclusive transfer of electrons down only one of the two parallel cofactor branches. In contrast to the RC core polypeptides (psaA and psaB) of photosystem I (PSI), where electron transfer occurs down both parallel redox-active cofactor branches, there is greater protein-cofactor asymmetry between the PSII RC core polypeptides (D1 and D2). We have focused on the identification of protein-cofactor relationships that determine the branch along which primary charge separation occurs (P680+/pheophytin-(Pheo)). We have previously shown that mutagenesis of the strong hydrogen-bonding residue, D1-E130, to less polar residues (D1-E130Q,H,L) shifted the midpoint potential of the PheoD1/PheoD1- couple to more negative values, reducing the quantum yield of primary charge separation. We did not observe, however, electron transfer down the inactive branch in D1-E130 mutants. The protein residue corresponding to D1-E130 on the inactive branch is D2-Q129 which presumably has a reduced hydrogen-bonding interaction with PheoD2 relative to the D1-E130 residue with PheoD1. Analysis of the recent 2.9 Å cyanobacterial PSII crystal structure indicated, however, that the D2-Q129 residue was too distant from the PheoD2 headgroup to serve as a possible hydrogen bond donor and directly impact its midpoint potential as well as potentially determine the directionality of electron transfer. Our objective was to characterize the function of this highly conserved inactive branch residue by replacing it with a nonconservative leucine or a conservative histidine residue. Measurements of Chl fluorescence decay kinetics and thermoluminescence studies indicate that the mutagenesis of D2-Q129 decreases the redox gap between QA and QB due to a lowering of the redox potential of QB. The

  4. Surface-Activated Coupling Reactions Confined on a Surface.

    PubMed

    Dong, Lei; Liu, Pei Nian; Lin, Nian

    2015-10-20

    Chemical reactions may take place in a pure phase of gas or liquid or at the interface of two phases (gas-solid or liquid-solid). Recently, the emerging field of "surface-confined coupling reactions" has attracted intensive attention. In this process, reactants, intermediates, and products of a coupling reaction are adsorbed on a solid-vacuum or a solid-liquid interface. The solid surface restricts all reaction steps on the interface, in other words, the reaction takes place within a lower-dimensional, for example, two-dimensional, space. Surface atoms that are fixed in the surface and adatoms that move on the surface often activate the surface-confined coupling reactions. The synergy of surface morphology and activity allow some reactions that are inefficient or prohibited in the gas or liquid phase to proceed efficiently when the reactions are confined on a surface. Over the past decade, dozens of well-known "textbook" coupling reactions have been shown to proceed as surface-confined coupling reactions. In most cases, the surface-confined coupling reactions were discovered by trial and error, and the reaction pathways are largely unknown. It is thus highly desirable to unravel the mechanisms, mechanisms of surface activation in particular, of the surface-confined coupling reactions. Because the reactions take place on surfaces, advanced surface science techniques can be applied to study the surface-confined coupling reactions. Among them, scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are the two most extensively used experimental tools. The former resolves submolecular structures of individual reactants, intermediates, and products in real space, while the latter monitors the chemical states during the reactions in real time. Combination of the two methods provides unprecedented spatial and temporal information on the reaction pathways. The experimental findings are complemented by theoretical modeling. In particular, density

  5. Electric field effects on the chlorophylls, pheophytins, and beta-carotenes in the reaction center of photosystem II.

    PubMed

    Frese, Raoul N; Germano, Marta; de Weerd, Frank L; van Stokkum, Ivo H M; Shkuropatov, Anatoli Ya; Shuvalov, Vladimir A; van Gorkom, Hans J; van Grondelle, Rienk; Dekker, Jan P

    2003-08-05

    We present an electric field modulated absorption spectroscopy (Stark effect) study of isolated photosystem II reaction center complexes, including a preparation in which the inactive pheophytin H(B) was exchanged for 13(1)-deoxo-13(1)-hydroxy-pheophytin. The results reveal that the Stark spectrum of the Q(x) and Q(y) transitions of the pheophytins has a second-derivative line shape, indicating that the Stark effect is dominated by differences in the dipole moment between the ground and the electronically excited states of these transitions (Delta mu). The Delta mu values for the Q(x) and Q(y) transitions of H(B) are small (Delta mu = 0.6-1.0 D f(-1)), whereas that of the Q(x) transition of the active pheophytin H(A) is remarkably large (Delta mu = 3 D f(-1)). The Stark spectrum of the red-most absorbing pigments also shows a second-derivative line shape, but this spectrum is considerably red-shifted as compared to the second derivative of the absorption spectrum. This situation is unusual but has been observed before in heterodimer special pair mutants of purple bacterial reaction centers [Moore, L. J., Zhou, H., and Boxer, S. G. (1999) Biochemistry 38, 11949-11960]. The red-shifted Stark spectra can be explained by a mixing of exciton states with a charge-transfer state of about equal energy. We conclude that the charge transfer state involves H(A) and its immediate chlorophyll neighbor (B(A)), and we suggest that this (B(A)(delta+)H(A)(delta-)) charge transfer state plays a crucial role in the primary charge separation reaction in photosystem II. In contrast to most other carotenes, the two beta-carotene molecules of the photosystem II reaction center display a very small Delta mu, which can most easily be explained by excitonic coupling of both molecules. These results favor a model that locates both beta-carotene molecules at the same side of the complex.

  6. On the possibility of negative activation energies in bimolecular reactions

    NASA Technical Reports Server (NTRS)

    Jaffe, R. L.

    1978-01-01

    The temperature dependence of the rate constants for model reacting systems was studied to understand some recent experimental measurements which imply the existence of negative activation energies. A collision theory model and classical trajectory calculations are used to demonstrate that the reaction probability can vary inversely with collision energy for bimolecular reactions occurring on attractive potential energy surfaces. However, this is not a sufficient condition to ensure that the rate constant has a negative temperature dependence. On the basis of these calculations, it seems unlikely that a true bimolecular reaction between neutral molecules will have a negative activation energy.

  7. Stereo and regioselectivity in ''Activated'' tritium reactions

    SciTech Connect

    Ehrenkaufer, R.L.E.; Hembree, W.C.; Wolf, A.P.

    1988-01-01

    To investigate the stereo and positional selectivity of the microwave discharge activation (MDA) method, the tritium labeling of several amino acids was undertaken. The labeling of L-valine and the diastereomeric pair L-isoleucine and L-alloisoleucine showed less than statistical labeling at the ..cap alpha..-amino C-H position mostly with retention of configuration. Labeling predominated at the single ..beta.. C-H tertiary (methyne) position. The labeling of L-valine and L-proline with and without positive charge on the ..cap alpha..-amino group resulted in large increases in specific activity (greater than 10-fold) when positive charge was removed by labeling them as their sodium carboxylate salts. Tritium NMR of L-proline labeled both as its zwitterion and sodium salt showed also large differences in the tritium distribution within the molecule. The distribution preferences in each of the charge states are suggestive of labeling by an electrophilic like tritium species(s). 16 refs., 5 tabs.

  8. Femtosecond infrared spectroscopy of reaction centers from Rhodobacter sphaeroides between 1000 and 1800 cm-1.

    PubMed Central

    Hamm, P; Zurek, M; Mäntele, W; Meyer, M; Scheer, H; Zinth, W

    1995-01-01

    Time-resolved pump-and-probe experiments of reaction centers of the purple bacterium Rhodobacter sphaeroides (R26) in the mid-IR region between 1000 and 1800 cm-1 are recorded with a time resolution of 300-400 fs. The difference spectra of the states P*, P+HA-, and P+QA- with respect to the ground state P predominantly reflect changes of the special pair. They show positive and negative bands due to changes of distinct vibrational modes superimposed on a broad background of enhanced absorption. A number of certain bands can be assigned to the special pair P, to the bacteriopheophytin HA, and to the quinone QA. The temporal evolution of the IR absorbance changes is well described by the time constants known from femtosecond spectroscopy of the electronic states. Differences occur only at very early times, which are indicative of fast vibrational relaxation with a time constant of a few hundred femtoseconds. PMID:7892185

  9. Mimicry of the radical pair and triplet states in photosynthetic reaction centers with a synthetic model

    SciTech Connect

    Hasharoni, K.; Levanon, H.; Greenfield, S.R.; Gosztola, D.J.; Svec, W.A.; Wasiclewski, M.R. |

    1995-08-02

    Supramolecular systems synthesized to model the photosynthetic reaction center (RC) are designed to mimic several key properties of the RC protein. Thus far, most RC models fulfill only a subset of these criteria, with very few reports employing time-resolved electron paramagnetic resonance spectroscopy (TREPR). We now report TREPR results on a photosynthetic model system (1) in a nematic liquid crystal (LC) that does not contain the natural pigments, yet closely mimics the spin dynamics of triplet state formation found only in photosynthetic RCs. The design of supermolecule 1 follows criteria established for promoting high quantum yield charge separation in glassy media. The observation of this triplet state in 1 by TREPR demonstrates that most of the electronic states found in the primary photochemistry of photosynthetic RCs can be mimicked successfully in synthetic models interacting with LCs. 12 refs., 3 figs.

  10. Geometry for the Primary Electron Donor and the Bacteriopheophytin Acceptor in Rhodopseudomonas viridis Photosynthetic Reaction Centers

    PubMed Central

    Tiede, D. M.; Choquet, Y.; Breton, J.

    1985-01-01

    The tetrapyrrole electron donors and acceptors (bacteriochlorophyll, BCh; bacteriopheophytin, BPh) within the bacterial photosynthetic reaction center (RC) are arranged with a specific geometry that permits rapid (picosecond time scale) electron tunneling to occur between them. Here we have measured the angle between the molecular planes of the bacteriochlorophyll dimer (primary donor), B2, and the acceptor bacteriopheophytin, H, by analyzing the dichroism of the absorption change associated with H reduction, formed by photoselection with RCs of Rhodopseudomonas viridis. This angle between molecular planes is found to be 60° ± 2. This means that the ultrafast electron tunneling must occur between donors and acceptors that are fixed by the protein to have a noncoplanar alignment. Nearly perpendicular alignments have been determined for other electron tunneling complexes involving RCs. These geometries can be contrasted with models proposed for heme-heme electron transfer complexes, which have emphasized that mutually parallel orientations should permit the most kinetically facile transfers. PMID:19431588

  11. Rate constants for aqueous-phase reactions of hydroxyl radical ({center_dot}OH) with aldehydes and ketones

    SciTech Connect

    Allen, J.M.; Allen, S.K.

    1995-12-31

    A wide variety of aldehydes and ketones are formed in the troposphere by the gas-phase oxidation of hydrocarbons. These compounds are expected to readily partition into cloud, fog, and aquated aerosol drops where they can participate in a variety of aqueous-phase reactions. It has been previously demonstrated by other researchers that aqueous-phase photochemical reactions involving aromatic aldehydes and ketones may lead to the formation of hydrogen peroxide. Hydrogen peroxide is an important oxidant for S(IV) and is also an {center_dot}OH precursor. Aldehydes and ketones may also participate in other aqueous-phase reactions within atmospheric water drops including reactions with {center_dot}OH. Rate constants for reactions involving {center_dot}OH in aqueous solutions have been reported for only a limited number of tropospheric aldehydes and ketones. The authors have measured the rate constants for aqueous-phase reactions of {center_dot}OH with several tropospheric aldehydes and ketones by the technique of competition kinetics. Hydroxyl radicals were generated by continuous illumination at 313 nm of an aqueous acidified solution containing Fe(ClO{sub 4}){sub 3}, an {center_dot}OH scavenger, the aldehyde or ketone whose rate constant was to be measured, and a standard for which the rate constant for reaction with {center_dot}OH is well known. Nitrobenzene was used as the standard in all experiments. Loss of the aldehyde or ketone and the standard were monitored by HPLC. Losses attributable to direct photolysis and dark reactions were minimal.

  12. Centers Made Simple: A Management and Activity Guide

    ERIC Educational Resources Information Center

    Reynolds, Laureen

    2005-01-01

    Drawing from her own experiences, teacher and author Laureen Reynolds shares management strategies, helpful suggestions, and quick tips to take the mystery out of setting up centers and demonstrates how to make the most of valuable classroom time. The activities outlined in this book are designed to appeal to students of all abilities, and range…

  13. Community Information and Services Centers: Concepts for Activation.

    ERIC Educational Resources Information Center

    Hopkins, Cleve

    An experimental program based on a study by the Department of Housing and Urban Development was activated to deliver services to urban residents via automated communications technology. Designed to contribute to improvement in the quality of life, the program of a Community Information and Services Center (CISC) included: outreach programs, i.e.,…

  14. AN OFF-CENTERED ACTIVE GALACTIC NUCLEUS IN NGC 3115

    SciTech Connect

    Menezes, R. B.; Steiner, J. E.; Ricci, T. V.

    2014-11-20

    NGC 3115 is an S0 galaxy that has always been considered to have a pure absorption-line spectrum. Some recent studies have detected a compact radio-emitting nucleus in this object, coinciding with the photometric center and with a candidate for the X-ray nucleus. This is evidence of the existence of a low-luminosity active galactic nucleus (AGN) in the galaxy, although no emission line has ever been observed. We report the detection of an emission-line spectrum of a type 1 AGN in NGC 3115, with an Hα luminosity of L {sub Hα} = (4.2 ± 0.4) × 10{sup 37} erg s{sup –1}. Our analysis revealed that this AGN is located at a projected distance of ∼0.''29 ± 0.''05 (corresponding to ∼14.3 ± 2.5 pc) from the stellar bulge center, which is coincident with the kinematic center of this object's stellar velocity map. The black hole corresponding to the observed off-centered AGN may form a binary system with a black hole located at the stellar bulge center. However, it is also possible that the displaced black hole is the merged remnant of the binary system coalescence, after the ''kick'' caused by the asymmetric emission of gravitational waves. We propose that certain features in the stellar velocity dispersion map are the result of perturbations caused by the off-centered AGN.

  15. Detection of photosynthetic energy storage in a photosystem I reaction center preparation by photoacoustic spectroscopy.

    PubMed

    Owens, T G; Carpentier, R; Leblanc, R M

    1990-06-01

    Thermal emission and photochemical energy storage were examined in photosystem I reaction center/core antenna complexes (about 40 Chl a/P700) using photoacoustic spectroscopy. Satisfactory signals could only be obtained from samples bound to hydroxyapatite and all samples had a low signal-to-noise ratio compared to either PS I or PS II in thylakoid membranes. The energy storage signal was saturated at low intensity (half saturation at 1.5 W m(-2)) and predicted a photochemical quantum yield of >90%. Exogenous donors and acceptors had no effect on the signal amplitudes indicating that energy storage is the result of charge separation between endogenous components. Fe(CN)6 (-3) oxidation of P700 and dithionite-induced reduction of acceptors FA-FB inhibited energy storage. These data are compatible with the hypothesis that energy storage in PS I arises from charge separation between P700 and Fe-S centers FA-FB that is stable on the time scale of the photoacoustic modulation. High intensity background light (160 W m(-2)) caused an irreversible loss of energy storage and correlated with a decrease in oxidizable P700; both are probably the result of high light-induced photoinhibition. By analogy to the low fluorescence yield of PS I, the low signal-to-noise ratio in these preparations is attributed to the short lifetime of Chl singlet excited states in PS I-40 and its indirect effect on the yield of thermal emission.

  16. Ex vivo engineered immune organoids for controlled germinal center reactions.

    PubMed

    Purwada, Alberto; Jaiswal, Manish K; Ahn, Haelee; Nojima, Takuya; Kitamura, Daisuke; Gaharwar, Akhilesh K; Cerchietti, Leandro; Singh, Ankur

    2015-09-01

    Ex vivo engineered three-dimensional organotypic cultures have enabled the real-time study and control of biological functioning of mammalian tissues. Organs of broad interest where its architectural, cellular, and molecular complexity has prevented progress in ex vivo engineering are the secondary immune organs. Ex vivo immune organs can enable mechanistic understanding of the immune system and more importantly, accelerate the translation of immunotherapies as well as a deeper understanding of the mechanisms that lead to their malignant transformation into a variety of B and T cell malignancies. However, till date, no modular ex vivo immune organ has been developed with an ability to control the rate of immune reaction through tunable design parameter. Here we describe a B cell follicle organoid made of nanocomposite biomaterials, which recapitulates the anatomical microenvironment of a lymphoid tissue that provides the basis to induce an accelerated germinal center (GC) reaction by continuously providing extracellular matrix (ECM) and cell-cell signals to naïve B cells. Compared to existing co-cultures, immune organoids provide a control over primary B cell proliferation with ∼100-fold higher and rapid differentiation to the GC phenotype with robust antibody class switching.

  17. Determination of the optimal position of adjacent proton-donor centers for the activation or inhibition of peptide bond formation--a computational model study.

    PubMed

    Rangelov, Miroslav A; Petrova, Galina P; Yomtova, Vihra M; Vayssilov, Georgi N

    2011-09-01

    The study reports a computational analysis of the influence of proton donor group adjacent to the reaction center during ester ammonolysis of an acylated diol as a model reaction for peptide bond formation. This analysis was performed using catalytic maps constructed after a detailed scanning of the available space around the reaction centers in different transition states, a water molecule acting as a typical proton donor. The calculations suggest that an adjacent proton donor center can reduce the activation barrier of the rate determining transition states by up to 7.2 kcal/mol, while no inhibition of the reaction can be achieved by such a group.

  18. PPARγ negatively regulates T cell activation to prevent follicular helper T cells and germinal center formation.

    PubMed

    Park, Hong-Jai; Kim, Do-Hyun; Choi, Jin-Young; Kim, Won-Ju; Kim, Ji Yun; Senejani, Alireza G; Hwang, Soo Seok; Kim, Lark Kyun; Tobiasova, Zuzana; Lee, Gap Ryol; Craft, Joseph; Bothwell, Alfred L M; Choi, Je-Min

    2014-01-01

    Peroxisome proliferator-activated receptor gamma (PPARγ) is a transcription factor that regulates lipid and glucose metabolism. Although studies of PPARγ ligands have demonstrated its regulatory functions in inflammation and adaptive immunity, its intrinsic role in T cells and autoimmunity has yet to be fully elucidated. Here we used CD4-PPARγKO mice to investigate PPARγ-deficient T cells, which were hyper-reactive to produce higher levels of cytokines and exhibited greater proliferation than wild type T cells with increased ERK and AKT phosphorylation. Diminished expression of IκBα, Sirt1, and Foxo1, which are inhibitors of NF-κB, was observed in PPARγ-deficient T cells that were prone to produce all the signature cytokines under Th1, Th2, Th17, and Th9 skewing condition. Interestingly, 1-year-old CD4-PPARγKO mice spontaneously developed moderate autoimmune phenotype by increased activated T cells, follicular helper T cells (TFH cells) and germinal center B cells with glomerular inflammation and enhanced autoantibody production. Sheep red blood cell immunization more induced TFH cells and germinal centers in CD4-PPARγKO mice and the T cells showed increased of Bcl-6 and IL-21 expression suggesting its regulatory role in germinal center reaction. Collectively, these results suggest that PPARγ has a regulatory role for TFH cells and germinal center reaction to prevent autoimmunity.

  19. Study of quark flow in exclusive reactions at 90 degrees in the center of mass (AGS E838)

    NASA Astrophysics Data System (ADS)

    Appel, R.; White, C.; Courant, H.; Fang, G.; Heller, K. J.; Johns, K.; Marshak, M. L.; Shupe, M.; Barton, D. S.; Bunce, G.; Carroll, A. S.; Gushue, S.; Kmit, M.; Lowenstein, D. I.; Makdisi, Y. I.; Heppelmann, S.; Ma, X.; Russell, J. J.

    1995-07-01

    We report a study of quark flow in 20 exclusive reactions measured at Brookhaven National Laboratory's AGS with a beam momentum of 5.9 GeV/c at 90° in the center of mass. This experiment confirms the strong quark flow reaction mechanism dependence of two-body hadron scattering at large angles seen at 9.9 GeV/c. Large differences in cross sections for different reactions are consistent with the dominance of quark interchange in these 90° reactions, and indicate that pure gluon exchange and quark/antiquark annihilation diagrams are less important.

  20. Magnetic circular dichroism investigation on chromophores in reaction centers of photosystem I and II of green plant photosynthesis

    NASA Astrophysics Data System (ADS)

    Nozawa, Tsunenori; Kobayashi, Masayuki; Wang, Zheng-Yu; Itoh, Shigeru; Iwaki, Masayo; Mimuro, Mamoru; Satoh, Kimiyuki

    1995-01-01

    Magnetic circular dichroism (MCD) of chlorophylls (Chl) in P700-enriched (12 Chl/P700) photosystem (PS) I particles and D1-D2-cyt b559 (PSII reaction center) particles isolated from spinach are measured in the wavelength region between 450 and 750 nm. The relative magnitude of MCD to absorption intensity ([MCD]/[Abs]) is found to be a good measure to estimate the interaction of chromophores (dimer or monomer). The difference spectrum between reduced and oxidized state for the 12 Chl/P700 particles can be interpreted to be composed of a positive MCD from P700 and a negative MCD for P700 +. MCD signals for the primary acceptor Chl a monomer (A 0) and the reduced cytochrome f are also observed. The MCD signal from pheophytin a in the PSII reaction center is remarkably in the Qx, region as strong as the signal from the reaction center chlorophylls (P680 and accessory) and other attached chlorophylls. Based on the data, the MCD bands, as well as the absorption bands in the Qy region, are deconvoluted into the contribution from reaction center chlorophylls and the other chlorophylls. The [MCD]/[Abs] ratio of P680 or P700 is small and similar to that of special pair bacteriochlorophylls in the reaction center of purple bacteria, indicating the specific feature of MCD signals that originate from a dimer-type interaction.

  1. Protein sequences and redox titrations indicate that the electron acceptors in reaction centers from heliobacteria are similar to Photosystem I

    NASA Technical Reports Server (NTRS)

    Trost, J. T.; Brune, D. C.; Blankenship, R. E.

    1992-01-01

    Photosynthetic reaction centers isolated from Heliobacillus mobilis exhibit a single major protein on SDS-PAGE of 47 000 Mr. Attempts to sequence the reaction center polypeptide indicated that the N-terminus is blocked. After enzymatic and chemical cleavage, four peptide fragments were sequenced from the Heliobacillus mobilis apoprotein. Only one of these sequences showed significant specific similarity to any of the protein and deduced protein sequences in the GenBank data base. This fragment is identical with 56% of the residues, including both cysteines, found in highly conserved region that is proposed to bind iron-sulfur center Fx in the Photosystem I reaction center peptide that is the psaB gene product. The similarity to the psaA gene product in this region is 48%. Redox titrations of laser-flash-induced photobleaching with millisecond decay kinetics on isolated reaction centers from Heliobacterium gestii indicate a midpoint potential of -414 mV with n = 2 titration behavior. In membranes, the behavior is intermediate between n = 1 and n = 2, and the apparent midpoint potential is -444 mV. This is compared to the behavior in Photosystem I, where the intermediate electron acceptor A1, thought to be a phylloquinone molecule, has been proposed to undergo a double reduction at low redox potentials in the presence of viologen redox mediators. These results strongly suggest that the acceptor side electron transfer system in reaction centers from heliobacteria is indeed analogous to that found in Photosystem I. The sequence similarities indicate that the divergence of the heliobacteria from the Photosystem I line occurred before the gene duplication and subsequent divergence that lead to the heterodimeric protein core of the Photosystem I reaction center.

  2. Large space antenna communications systems: Integrated Langley Research Center/Jet Propulsion Laboratory development activities. 2: Langley Research Center activities

    NASA Technical Reports Server (NTRS)

    Cambell, T. G.; Bailey, M. C.; Cockrell, C. R.; Beck, F. B.

    1983-01-01

    The electromagnetic analysis activities at the Langley Research Center are resulting in efficient and accurate analytical methods for predicting both far- and near-field radiation characteristics of large offset multiple-beam multiple-aperture mesh reflector antennas. The utilization of aperture integration augmented with Geometrical Theory of Diffraction in analyzing the large reflector antenna system is emphasized.

  3. Femtosecond activation of reactions and the concept of nonergodic molecules

    PubMed

    Diau; Herek; Kim; Zewail

    1998-02-06

    The description of chemical reaction dynamics often assumes that vibrational modes are well coupled (ergodic) and redistribute energy rapidly with respect to the course of the reaction. To experimentally probe nonergodic, nonstatistical behavior, studies of a series of reactions induced by femtosecond activation for molecules of varying size but having the same reaction coordinates [CH2 - (CH2)n-2 - C = Odagger --> products, with n = 4, 5, 6, and 10] were performed. Comparison of the experimental results with theoretical electronic structure and rate calculations showed a two to four orders of magnitude difference, indicating that the basic assumption of statistical energy redistribution is invalid. These results suggest that chemical selectivity can be achieved with femtosecond activation even at very high energies.

  4. Climate Change Adaptation Science Activities at NASA Johnson Space Center

    NASA Technical Reports Server (NTRS)

    Stefanov, William L.; Lulla, Kamlesh

    2012-01-01

    The Johnson Space Center (JSC), located in the southeast metropolitan region of Houston, TX is the prime NASA center for human spaceflight operations and astronaut training, but it also houses the unique collection of returned extraterrestrial samples, including lunar samples from the Apollo missions. The Center's location adjacent to Clear Lake and the Clear Creek watershed, an estuary of Galveston Bay, puts it at direct annual risk from hurricanes, but also from a number of other climate-related hazards including drought, floods, sea level rise, heat waves, and high wind events all assigned Threat Levels of 2 or 3 in the most recent NASA Center Disaster/Risk Matrix produced by the Climate Adaptation Science Investigator Working Group. Based on prior CASI workshops at other NASA centers, it is recognized that JSC is highly vulnerable to climate-change related hazards and has a need for adaptation strategies. We will present an overview of prior CASI-related work at JSC, including publication of a climate change and adaptation informational data brochure, and a Resilience and Adaptation to Climate Risks Workshop that was held at JSC in early March 2012. Major outcomes of that workshop that form a basis for work going forward are 1) a realization that JSC is embedded in a regional environmental and social context, and that potential climate change effects and adaptation strategies will not, and should not, be constrained by the Center fence line; 2) a desire to coordinate data collection and adaptation planning activities with interested stakeholders to form a regional climate change adaptation center that could facilitate interaction with CASI; 3) recognition that there is a wide array of basic data (remotely sensed, in situ, GIS/mapping, and historical) available through JSC and other stakeholders, but this data is not yet centrally accessible for planning purposes.

  5. B-H bond activation using an electrophilic metal complex: insights into the reaction pathway.

    PubMed

    Kumar, Rahul; Jagirdar, Balaji R

    2013-01-07

    A highly electrophilic ruthenium center in the [RuCl(dppe)(2)][OTf] complex brings about the activation of the B-H bond in ammonia borane (H(3)N·BH(3), AB) and dimethylamine borane (Me(2)HN·BH(3), DMAB). At room temperature, the reaction between [RuCl(dppe)(2)][OTf] and AB or DMAB results in trans-[RuH(η(2)-H(2))(dppe)(2)][OTf], trans-[RuCl(η(2)-H(2))(dppe)(2)][OTf], and trans-[RuH(Cl)(dppe)(2)], as noted in the NMR spectra. Mixing the ruthenium complex and AB or DMAB at low temperature (198/193 K) followed by NMR spectral measurements as the reaction mixture was warmed up to room temperature allowed the observation of various species formed enroute to the final products that were obtained at room temperature. On the basis of the variable-temperature multinuclear NMR spectroscopic studies of these two reactions, the mechanistic insights for B-H bond activation were obtained. In both cases, the reaction proceeds via an η(1)-B-H moiety bound to the metal center. The detailed mechanistic pathways of these two reactions as studied by NMR spectroscopy are described.

  6. Vehicle Engineering Development Activities at the Marshall Space Flight Center

    NASA Technical Reports Server (NTRS)

    Fisher, Mark F.; Champion, Robert H., Jr.

    1999-01-01

    New initiatives in the Space Transportation Directorate at the Marshall Space Flight Center include an emphasis on Vehicle Engineering to enhance the strong commitment to the Directorate's projects in the development of flight hardware and flight demonstrators for the advancement of space transportation technology. This emphasis can be seen in the activities of a newly formed organization in the Transportation Directorate, The Vehicle Subsystems Engineering Group. The functions and type of activities that this group works on are described. The current projects of this group are outlined including a brief description of the status and type of work that the group is performing. A summary section is included to describe future activities.

  7. Highly Stable and Active Catalyst for Sabatier Reactions

    NASA Technical Reports Server (NTRS)

    Hu, Jianli; Brooks, Kriston P.

    2012-01-01

    Highly active Ru/TiO2 catalysts for Sabatier reaction have been developed. The catalysts have shown to be stable under repeated shutting down/startup conditions. When the Ru/TiO2 catalyst is coated on the engineered substrate Fe-CrAlY felt, activity enhancement is more than doubled when compared with an identically prepared engineered catalyst made from commercial Degussa catalyst. Also, bimetallic Ru-Rh/TiO2 catalysts show high activity at high throughput.

  8. Contributions of parent molecule fixed and excess energies to product energy partitioning in four-center elimination reactions

    NASA Astrophysics Data System (ADS)

    Benito, R. M.; Santamaría, J.

    1989-03-01

    In four-center elimination reactions such as hydrogen halide elimination from halogenated hydrocarbons the energy barrier is higher than the difference in enthalpy of formation between the parent molecule and its fragments (HX and olefin). This determines that the energy available to products has two origins: the reverse reaction barrier (fixed energy), and the excess energy (energy above the barrier). Both types of energy are partitioned among products following different laws: more or less statistical for excess energy and non-statistical for fixed energy. In a study of CF 3-CH 3 decomposition, we describe a practical method, based on the variation of product energy partitioning with excess energy, to determine the partitioning of the fixed energy among different types of product energy, thus defining the exact nature of the reverse reaction energy barrier. We applied this model to other types of reactions, such as three-center molecular eliminations.

  9. O2 activation by binuclear Cu sites: Noncoupled versus exchange coupled reaction mechanisms

    NASA Astrophysics Data System (ADS)

    Chen, Peng; Solomon, Edward I.

    2004-09-01

    Binuclear Cu proteins play vital roles in O2 binding and activation in biology and can be classified into coupled and noncoupled binuclear sites based on the magnetic interaction between the two Cu centers. Coupled binuclear Cu proteins include hemocyanin, tyrosinase, and catechol oxidase. These proteins have two Cu centers strongly magnetically coupled through direct bridging ligands that provide a mechanism for the 2-electron reduction of O2 to a µ-2:2 side-on peroxide bridged species. This side-on bridged peroxo-CuII2 species is activated for electrophilic attack on the phenolic ring of substrates. Noncoupled binuclear Cu proteins include peptidylglycine -hydroxylating monooxygenase and dopamine -monooxygenase. These proteins have binuclear Cu active sites that are distant, that exhibit no exchange interaction, and that activate O2 at a single Cu center to generate a reactive CuII/O2 species for H-atom abstraction from the C-H bond of substrates. O2 intermediates in the coupled binuclear Cu enzymes can be trapped and studied spectroscopically. Possible intermediates in noncoupled binuclear Cu proteins can be defined through correlation to mononuclear CuII/O2 model complexes. The different intermediates in these two classes of binuclear Cu proteins exhibit different reactivities that correlate with their different electronic structures and exchange coupling interactions between the binuclear Cu centers. These studies provide insight into the role of exchange coupling between the Cu centers in their reaction mechanisms.

  10. Corrosion Activities at the NASA Kennedy Space Center

    NASA Technical Reports Server (NTRS)

    Heidersbach, Robert H.

    2002-01-01

    This report documents summer faculty fellow efforts in the corrosion test bed at the NASA Kennedy Space Center. During the summer of 2002 efforts were concentrated on three activities: a short course on corrosion control for KSC personnel, evaluation of commercial wash additives used for corrosion control on Army aircraft, and improvements in the testing of a new cathodic protection system under development at KSC.

  11. Rates of primary electron transfer reactions in the photosystem I reaction center reconstituted with different quinones as the secondary acceptor

    SciTech Connect

    Kumazaki, Shigeichi; Kandori, Hideki; Yoshihara, Keitaro ); Iwaki, Masayo; Itoh, Shigeru ); Ikegamu, Isamu )

    1994-10-27

    Rates of sequential electron transfer reactions from the primary electron donor chlorophyll dimer (P700) to the electron acceptor chlorophyll a-686 (A[sub 0]) and to the secondary acceptor quinone (Q[sub [phi

  12. Force-activated reactivity switch in a bimolecular chemical reaction.

    PubMed

    Garcia-Manyes, Sergi; Liang, Jian; Szoszkiewicz, Robert; Kuo, Tzu-Ling; Fernández, Julio M

    2009-06-01

    The effect of mechanical force on the free-energy surface that governs a chemical reaction is largely unknown. The combination of protein engineering with single-molecule force-clamp spectroscopy allows us to study the influence of mechanical force on the rate at which a protein disulfide bond is reduced by nucleophiles in a bimolecular substitution reaction (S(N)2). We found that cleavage of a protein disulfide bond by hydroxide anions exhibits an abrupt reactivity 'switch' at ∼500 pN, after which the accelerating effect of force on the rate of an S(N)2 chemical reaction greatly diminishes. We propose that an abrupt force-induced conformational change of the protein disulfide bond shifts its ground state, drastically changing its reactivity in S(N)2 chemical reactions. Our experiments directly demonstrate the action of a force-activated switch in the chemical reactivity of a single molecule.

  13. Infrared Detector Activities at NASA Langley Research Center

    NASA Technical Reports Server (NTRS)

    Abedin, M. N.; Refaat, T. F.; Sulima, O. V.; Amzajerdian, F.

    2008-01-01

    Infrared detector development and characterization at NASA Langley Research Center will be reviewed. These detectors were intended for ground, airborne, and space borne remote sensing applications. Discussion will be focused on recently developed single-element infrared detector and future development of near-infrared focal plane arrays (FPA). The FPA will be applied to next generation space-based instruments. These activities are based on phototransistor and avalanche photodiode technologies, which offer high internal gain and relatively low noise-equivalent-power. These novel devices will improve the sensitivity of active remote sensing instruments while eliminating the need for a high power laser transmitter.

  14. NASA Stennis Space Center Test Technology Branch Activities

    NASA Technical Reports Server (NTRS)

    Solano, Wanda M.

    2000-01-01

    This paper provides a short history of NASA Stennis Space Center's Test Technology Laboratory and briefly describes the variety of engine test technology activities and developmental project initiatives. Theoretical rocket exhaust plume modeling, acoustic monitoring and analysis, hand held fire imaging, heat flux radiometry, thermal imaging and exhaust plume spectroscopy are all examples of current and past test activities that are briefly described. In addition, recent efforts and visions focused on accomodating second, third, and fourth generation flight vehicle engine test requirements are discussed.

  15. Characterization of a Rhodobacter capsulatus reaction center mutant that enhances the distinction between spectral forms of the initial electron donor.

    PubMed

    Eastman, J E; Taguchi, A K; Lin, S; Jackson, J A; Woodbury, N W

    2000-12-05

    A large scale mutation of the Rhodobacter capsulatus reaction center M-subunit gene, sym2-1, has been constructed in which amino acid residues M205-M210 have been changed to the corresponding L subunit amino acids. Two interconvertable spectral forms of the initial electron donor are observed in isolated reaction centers from this mutant. Which conformation dominates depends on ionic strength, the nature of the detergent used, and the temperature. Reaction centers from this mutant have a ground-state absorbance spectrum that is very similar to wild-type when measured immediately after purification in the presence of high salt. However, upon subsequent dialysis against a low ionic strength buffer or the addition of positively charged detergents, the near-infrared spectral band of P (the initial electron donor) in sym2-1 reaction centers is shifted by over 30 nm to the blue, from 852 to 820 nm. Systematically varying either the ionic strength or the amount of charged detergent reveals an isobestic point in the absorbance spectrum at 845 nm. The wild-type spectrum also shifts with ionic strength or detergent with an isobestic point at 860 nm. The large spectral separation between the two dominant conformational forms of the sym2-1 reaction center makes detailed measurements of each state possible. Both of the spectral forms of P bleach in the presence of light. Electrochemical measurements of the P/P+ midpoint potential of sym2-1 reaction centers show an increase of about 30 mV upon conversion from the long-wavelength form to the short-wavelength form of the mutant. The rate constant of initial electron transfer in both forms of the mutant reaction centers is essentially the same, suggesting that the spectral characteristics of P are not critical for charge separation. The short-wavelength form of P in this mutant also converts to the long-wavelength form as a function of temperature between room temperature and 130 K, again giving rise to an isobestic point, in this

  16. Excited state dynamics in photosynthetic reaction center and light harvesting complex 1

    NASA Astrophysics Data System (ADS)

    Strümpfer, Johan; Schulten, Klaus

    2012-08-01

    Key to efficient harvesting of sunlight in photosynthesis is the first energy conversion process in which electronic excitation establishes a trans-membrane charge gradient. This conversion is accomplished by the photosynthetic reaction center (RC) that is, in case of the purple photosynthetic bacterium Rhodobacter sphaeroides studied here, surrounded by light harvesting complex 1 (LH1). The RC employs six pigment molecules to initiate the conversion: four bacteriochlorophylls and two bacteriopheophytins. The excited states of these pigments interact very strongly and are simultaneously influenced by the surrounding thermal protein environment. Likewise, LH1 employs 32 bacteriochlorophylls influenced in their excited state dynamics by strong interaction between the pigments and by interaction with the protein environment. Modeling the excited state dynamics in the RC as well as in LH1 requires theoretical methods, which account for both pigment-pigment interaction and pigment-environment interaction. In the present study we describe the excitation dynamics within a RC and excitation transfer between light harvesting complex 1 (LH1) and RC, employing the hierarchical equation of motion method. For this purpose a set of model parameters that reproduce RC as well as LH1 spectra and observed oscillatory excitation dynamics in the RC is suggested. We find that the environment has a significant effect on LH1-RC excitation transfer and that excitation transfers incoherently between LH1 and RC.

  17. Microaerophilic growth and induction of the photosynthetic reaction center in Rhodopseudomonas viridis

    SciTech Connect

    Lang, F.S.; Oesterhelt, D.

    1989-05-01

    Rhodopseudomonas viridis was grown in liquid culture at 30 degrees C anaerobically in light (generation time, 13 h) and under microaerophilic growth conditions in the dark (generation time, 24 h). The bacterium could be cloned at the same temperature anaerobically in light (1 week) and aerobically in the dark (3 to 4 weeks) if oxygen was limited to 0.1%. Oxygen could not be replaced by dimethyl sulfoxide, potassium nitrate, or sodium nitrite as a terminal electron acceptor. No growth was observed anaerobically in darkness or in the light when air was present. A variety of additional carbon sources were used to supplement the standard succinate medium, but enhanced stationary-phase cell density was observed only with glucose. Conditions for induction of the photosynthetic reaction center upon the change from microaerophilic to phototrophic growth conditions were investigated and optimized for a mutant functionally defective in phototrophic growth. R. viridis consumed about 20-fold its cell volume of oxygen per hour during respiration. The MICs of ampicillin, kanamycin, streptomycin, tetracycline, 1-methyl-3-nitro-1-nitrosoguanidine, and terbutryn were determined.

  18. On the nature of excited states of photosynthetic reaction centers: An ultrafast infrared study

    SciTech Connect

    Haran, G.; Wynne, K.; Reid, G.D.

    1995-12-31

    Bacterial photosynthetic reaction centers (RC) contain eight chromophores forming a well-defined supramolecular structure within a protein framework. Theoretical studies suggest that the excited states of these chromophores are delocalized and contain important contributions from charge-transfer and resonance states. There is no clear-cut experimental evidence pertaining to the degree of localization of excited states. We have used ultrafast near and mid-infrared spectroscopic methods to investigate the character of some of the excited states. Exciting the 800 nm, absorption band, we followed the fate of the excitation energy using either the stimulated emission of the special pair at 920 nm or a transient absorption at 1.2 {mu}m. For a completely localized system, Forster theory-based calculations are expected to accurately predict the kinetics of energy transfer. It was found, however, that calculated rates arc much faster than measured rates. This corroborates a delocalized picture, with internal conversion rather than energy transfer between states. We have also measured the transient absorption spectrum of the RC in the infrared spectral region, detecting several new low-lying electronic states. Assignments for these states, and implications for the localization problem will be discussed.

  19. Orientated binding of photosynthetic reaction centers on gold using Ni-NTA self-assembled monolayers.

    PubMed

    Trammell, Scott A; Wang, Leyu; Zullo, Joseph M; Shashidhar, Ranganathan; Lebedev, Nikolai

    2004-07-15

    Coupling of photosynthetic reaction centers (RCs) with inorganic surfaces is attractive for the identification of the mechanisms of interprotein electron transfer (ET) and for possible applications in construction of photo- and chemosensors. Here we show that RCs from Rhodobacter sphaeroides can be immobilized on gold surfaces with the RC primary donor looking towards the substrate by using a genetically engineered poly-histidine tag (His(7)) at the C-terminal end of the M-subunit and a Ni-NTA terminated self-assembled monolayer (SAM). In the presence of an electron acceptor, ubiquinone-10, illumination of this RC electrode generates a cathodic photocurrent. The action spectrum of the photocurrent coincides with the absorption spectrum of RC and the photocurrent decreases in response to the herbicide, atrazine, confirming that the RC is the primary source of the photoresponse. Disruption of the Ni-NTA-RC bond by imidazole leads to about 80% reduction of the photocurrent indicating that most of the photoactive protein is specifically bound to the electrode through the linker.

  20. Temporal and spectral characterization of the photosynthetic reaction center from Heliobacterium modesticaldum.

    PubMed

    Chauvet, Adrien; Sarrou, Josephine; Lin, Su; Romberger, Steven P; Golbeck, John H; Savikhin, Sergei; Redding, Kevin E

    2013-09-01

    A time-resolved spectroscopic study of the isolated photosynthetic reaction center (RC) from Heliobacterium modesticaldum reveals that thermal equilibration of light excitation among the antenna pigments followed by trapping of excitation and the formation of the charge-separated state P800 (+)A0 (-) occurs within ~25 ps. This time scale is similar to that reported for plant and cyanobacterial photosystem I (PS I) complexes. Subsequent electron transfer from the primary electron acceptor A0 occurs with a lifetime of ~600 ps, suggesting that the RC of H. modesticaldum is functionally similar to that of Heliobacillus mobilis and Heliobacterium chlorum. The (A0 (-) - A0) and (P800 (+) - P800) absorption difference spectra imply that an 8(1)-OH-Chl a F molecule serves as the primary electron acceptor and occupies the position analogous to ec3 (A0) in PS I, while a monomeric BChl g pigment occupies the position analogous to ec2 (accessory Chl). The presence of an intense photobleaching band at 790 nm in the (A0 (-) - A0) spectrum suggests that the excitonic coupling between the monomeric accessory BChl g and the 8(1)-OH-Chl a F in the heliobacterial RC is significantly stronger than the excitonic coupling between the equivalent pigments in PS I.

  1. Redox potential tuning through differential quinone binding in the photosynthetic reaction center of Rhodobacter sphaeroides

    DOE PAGES

    Vermaas, Josh V.; Taguchi, Alexander T.; Dikanov, Sergei A.; ...

    2015-03-03

    Ubiquinone forms an integral part of the electron transport chain in cellular respiration and photosynthesis across a vast number of organisms. Prior experimental results have shown that the photosynthetic reaction center (RC) from Rhodobacter sphaeroides is only fully functional with a limited set of methoxy-bearing quinones, suggesting that specific interactions with this substituent are required to drive electron transport and the formation of quinol. The nature of these interactions has yet to be determined. Through parameterization of a CHARMM-compatible quinone force field and subsequent molecular dynamics simulations of the quinone-bound RC, in this paper we have investigated and characterized themore » interactions of the protein with the quinones in the QA and QB sites using both equilibrium simulation and thermodynamic integration. In particular, we identify a specific interaction between the 2-methoxy group of ubiquinone in the QB site and the amide nitrogen of GlyL225 that we implicate in locking the orientation of the 2-methoxy group, thereby tuning the redox potential difference between the quinones occupying the QA and QB sites. Finally, disruption of this interaction leads to weaker binding in a ubiquinone analogue that lacks a 2-methoxy group, a finding supported by reverse electron transfer electron paramagnetic resonance experiments of the QA–QB– biradical and competitive binding assays.« less

  2. Spectral, photophysical, and stability properties of isolated photosystem II reaction center

    SciTech Connect

    Seibert, M.; Picorel, R.; Rubin, A.B.; Connolly, J.S. )

    1988-06-01

    Photosystem II reaction center (RC) preparations isolated from spinach (Spinacea oleracea) by the Nanba-Satoh procedure are quite labile, even at 4{degree}C in the dark. Simple spectroscopic criteria were developed to characterize the native state of the material. Degradation of the RC results in (a) blue-shifting of the red-most absorption maximum, (b) a shift of the 77 K fluorescence maximum from {approximately}682 nm to {approximately}670 nm, and (c) a shift of fluorescence lifetime components from 1.3-4 nanoseconds and >25 nanoseconds to {approximately}6-7 nanoseconds. Fluorescence properties at 77 K seem to be a more sensitive spectral indicator of the integrity of the material. The >25 nanosecond lifetime component is assigned to P680{sup +} Phenophytin{sup -}recombination luminescence, which suggest a correlation between the observed spectral shifts and the photochemical competence of the preparation. Substitution of lauryl maltoside for Triton X-100 immediately after RC isolation stabilizes the RCs and suggests that Triton may be responsible for the instability.

  3. Structural and preliminary molecular dynamics studies of the Rhodobacter sphaeroides reaction center and its mutant form L(M196)H + H(M202)L

    NASA Astrophysics Data System (ADS)

    Klyashtorny, V. G.; Fufina, T. Yu.; Vasilieva, L. G.; Shuvalov, V. A.; Gabdulkhakov, A. G.

    2014-07-01

    Pigment-protein interactions are responsible for the high efficiency of the light-energy transfer and conversion in photosynthesis. The reaction center (RC) from the purple bacterium Rhodobacter sphaeroides is the most convenient model for studying the mechanisms of primary processes of photosynthesis. Site-directed mutagenesis can be used to study the effect of the protein environment of electron-transfer cofactors on the optical properties, stability, pigment composition, and functional activity of RC. The preliminary analysis of RC was performed by computer simulation of the amino acid substitutions L(M196)H + H(M202)L at the pigment-protein interface and by estimating the stability of the threedimensional structure of the mutant RC by the molecular dynamics method. The doubly mutated reaction center was overexpressed, purified, and crystallized. The three-dimensional structure of this mutant was determined by X-ray crystallography and compared with the molecular dynamics model.

  4. Oxygen activation by mononuclear Mn, Co, and Ni centers in biology and synthetic complexes.

    PubMed

    Fiedler, Adam T; Fischer, Anne A

    2017-04-01

    The active sites of metalloenzymes that catalyze O2-dependent reactions generally contain iron or copper ions. However, several enzymes are capable of activating O2 at manganese or nickel centers instead, and a handful of dioxygenases exhibit activity when substituted with cobalt. This minireview summarizes the catalytic properties of oxygenases and oxidases with mononuclear Mn, Co, or Ni active sites, including oxalate-degrading oxidases, catechol dioxygenases, and quercetin dioxygenase. In addition, recent developments in the O2 reactivity of synthetic Mn, Co, or Ni complexes are described, with an emphasis on the nature of reactive intermediates featuring superoxo-, peroxo-, or oxo-ligands. Collectively, the biochemical and synthetic studies discussed herein reveal the possibilities and limitations of O2 activation at these three "overlooked" metals.

  5. Air oxidation of hydrazine. 1. Reaction kinetics on natural kaolinites, halloysites, and model substituent layers with varying iron and titanium oxide and O- center contents

    NASA Technical Reports Server (NTRS)

    Coyne, L.; Mariner, R.; Rice, A.

    1991-01-01

    Air oxidation of hydrazine was studied by using a group of kaolinites, halloysites, and substituent oxides as models for the tetrahedral and octahedral sheets. The rate was found to be linear with oxygen. The stoichiometry showed that oxygen was the primary oxidant and that dinitrogen was the only important nitrogen-containing product. The rates on kaolinites were strongly inhibited by water. Those on three-dimensional silica and gibbsite appeared not to be. That on a supposedly layered silica formed from a natural kaolinite by acid leaching showed transitional behavior--slowed relative to that expected from a second-order reaction relative to that on the gibbsite and silica but faster than those on the kaolinites. The most striking result of the reaction was the marked increase in the rate of reaction of a constant amount of hydrazine as the amount of clay was increased. The increase was apparent (in spite of the water inhibition at high conversions) over a 2 order of magnitude variation of the clay weight. The weight dependence was taken to indicate that the role of the clay is very important, that the number of reactive centers is very small, or that they may be deactivated over the course of the reaction. In contrast to the strong dependence on overall amount of clay, the variation of amounts of putative oxidizing centers, such as structural Fe(III), admixed TiO2 or Fe2O3, or O- centers, did not result in alteration of the rate commensurate with the degree of variation of the entity in question. Surface iron does play some role, however, as samples that were pretreated with a reducing agent were less active as catalysts than the parent material. These results were taken to indicate either that the various centers interact to such a degree that they cannot be considered independently or that the reaction might proceed by way of surface complexation, rather than single electron transfers.

  6. Caffeine enhances micturition through neuronal activation in micturition centers.

    PubMed

    Cho, Young-Sam; Ko, Il-Gyu; Kim, Sung-Eun; Hwan, Lakkyong; Shin, Mal-Soon; Kim, Chang-Ju; Kim, Sang-Hoon; Jin, Jun-Jang; Chung, Jun-Young; Kim, Khae-Hawn

    2014-12-01

    Caffeine may promote incontinence through its diuretic effect, particularly in individuals with underlying detrusor overactivity, in addition to increasing muscle contraction of the bladder smooth muscle. Caffeine may also affect bladder function via central micturition centers, including the medial preoptic area, ventrolateral periaqueductal gray, and pontine micturition center. However, the biochemical mechanisms of caffeine in central micturition centers affecting bladder function remain unclear. In the present study, the effects of caffeine on the central micturition reflex were investigated by measuring the degree of neuronal activation, and by quantifying nerve growth factor (NGF) expression in rats. Following caffeine administration for 14 days, a urodynamic study was performed to assess the changes to bladder function. Subsequently, immunohistochemical staining to identify the expression of c‑Fos and NGF in the central micturition areas was performed. Ingestion of caffeine increased bladder smooth muscle contraction pressure and time as determined by cystometry. Expression levels of c‑Fos and NGF in all central micturition areas were significantly increased following the administration of caffeine. The effects on contraction pressure and time were the most potent and expression levels of c‑Fos and NGF were greatest at the lowest dose of caffeine. These results suggest that caffeine facilitates bladder instability through enhancing neuronal activation in the central micturition areas.

  7. Reactions of oxidatively activated arylamines with thiols: reaction mechanisms and biologic implications. An overview.

    PubMed Central

    Eyer, P

    1994-01-01

    Aromatic amines belong to a group of compounds that exert their toxic effects usually after oxidative biotransformation, primarily in the liver. In addition, aromatic amines also undergo extrahepatic activation to yield free arylaminyl radicals. The reactive intermediates are potential promutagens and procarcinogens, and responsible for target tissue toxicity. Since thiols react with these intermediates at high rates, it is of interest to know the underlying reaction mechanisms and the toxicologic implications. Phenoxyl radicals from aminophenols and aminyl radicals from phenylenediamines quickly disproportionate to quinone imines and quinone diimines. Depending on the structure, Michael addition or reduction reactions with thiols may prevail. Products of sequential oxidation/addition reactions (e.g., S-conjugates of aminophenols) are occasionally more toxic than the parent compounds because of their higher autoxidizability and their accumulation in the kidney. Even after covalent binding of quinone imines to protein SH groups, the resulting thioethers are able to autoxidize. The quinoid thioethers can then cross-link the protein by addition to neighboring nucleophiles. The reactions of nitrosoarenes with thiols yield a so-called "semimercaptal" from which various branching reactions detach, depending on substituents. Compounds with strong pi-donors, like 4-nitrosophenetol, give a resonance-stabilized N-(thiol-S-yl)-arylamine cation that may lead to bicyclic products, thioethers, and DNA adducts. Examples of toxicologic implications of the interactions of nitroso compounds with thiols are given for nitrosoimidazoles, heterocyclic nitroso compounds from protein pyrolysates, and nitrosoarenes. These data indicate that interactions of activated arylamines with thiols may not be regarded exclusively as detoxication reactions. PMID:7889834

  8. Data Information for Global Change Studies: NASA's Distributed Active Archive Centers and Cooperating Data Centers

    NASA Technical Reports Server (NTRS)

    2000-01-01

    The Earth Observing System (EOS) is an integral part of the National Aeronautics and Space Administration's (NASA's) Earth Science Enterprise (ESE). ESE is a long-term global change research program designed to improve our understanding of the Earth's interrelated processes involving the atmosphere, oceans, land surfaces, and polar regions. Data from EOS instruments and other Earth science measurement systems are useful in understanding the causes and processes of global climate change and the consequences of human activities. The EOS Data and Information System (EOSDIS) provides a structure for data management and user services for products derived from EOS satellite instruments and other NASA Earth science data. Within the EOSDIS framework, the Distributed Active Archive Centers (DAACs) have been established to provide expertise in one or more Earth science disciplines. The DAACs and cooperating data centers provide data and information services to support the global change research community. Much of the development of the DAACs has been in anticipation of the enormous amount of data expected from EOS instruments to be launched within the next two decades. Terra, the EOS flagship launched in December 1999, is the first of a series of EOS satellites to carry several instruments with multispectral capabilities. Some data products from these instruments are now available from several of the DAACs. These and other data products can be ordered through the EOS Data Gateway (EDG) and DAAC-specific online ordering systems.

  9. Ligand reorganization and activation energies in nonadiabatic electron transfer reactions

    NASA Astrophysics Data System (ADS)

    Zhu, Jianjun; Wang, Jianji; Stell, George

    2006-10-01

    The activation energy and ligand reorganization energy for nonadiabatic electron transfer reactions in chemical and biological systems are investigated in this paper. The free energy surfaces and the activation energy are derived exactly in the general case in which the ligand vibration frequencies are not equal. The activation energy is derived by free energy minimization at the transition state. Our formulation leads to the Marcus-Hush [J. Chem. Phys. 24, 979 (1956); 98, 7170 (1994); 28, 962 (1958)] results in the equal-frequency limit and also generalizes the Marcus-Sumi [J. Chem. Phys. 84, 4894 (1986)] model in the context of studying the solvent dynamic effect on electron transfer reactions. It is found that when the ligand vibration frequencies are different, the activation energy derived from the Marcus-Hush formula deviates by 5%-10% from the exact value. If the reduced reorganization energy approximation is introduced in the Marcus-Hush formula, the result is almost exact.

  10. Blockade of STAT3 in T Cells Inhibits Germinal Center Reactions against Intranasal Allergens.

    PubMed

    Choi, Garam; Chung, Yeonseok

    2016-05-01

    Understanding the developmental mechanisms of humoral immunity against intranasal antigens is essential for the development of therapeutic approaches against air-borne pathogens as well as allergen-induced pulmonary inflammation. Follicular helper T (Tfh) cells expressing CXCR5 are required for humoral immunity by providing IL-21 and ICOS costimulation to activated B cells. However, the regulation of Tfh cell responses against intranasal antigens remains unclear. Here, we found that the generation of Tfh cells and germinal center B cells in the bronchial lymph node against intranasal proteinase antigens was independent of TGF-β. In contrast, administration of STAT3 inhibitor STA-21 suppressed the generation of Tfh cells and germinal center B cells. Compared with wild-type OT-II T cells, STAT3-deficient OT-II T cells transferred into recipients lacking T cells not only showed significantly reduced frequency Tfh cells, but also induced diminished IgG as well as IgE specific for the intranasal antigens. Cotransfer study of wild-type OT-II and STAT3-deficient OT-II T cells revealed that the latter failed to differentiate into Tfh cells. These findings demonstrate that T cell-intrinsic STAT3 is required for the generation of Tfh cells to intranasal antigens and that targeting STAT3 might be an effective approach to ameliorate antibody-mediated pathology in the lung.

  11. Land processes distributed active archive center product lifecycle plan

    USGS Publications Warehouse

    Daucsavage, John C.; Bennett, Stacie D.

    2014-01-01

    The U.S. Geological Survey (USGS) Earth Resources Observation and Science (EROS) Center and the National Aeronautics and Space Administration (NASA) Earth Science Data System Program worked together to establish, develop, and operate the Land Processes (LP) Distributed Active Archive Center (DAAC) to provide stewardship for NASA’s land processes science data. These data are critical science assets that serve the land processes science community with potential value beyond any immediate research use, and therefore need to be accounted for and properly managed throughout their lifecycle. A fundamental LP DAAC objective is to enable permanent preservation of these data and information products. The LP DAAC accomplishes this by bridging data producers and permanent archival resources while providing intermediate archive services for data and information products.

  12. GHRC: NASAs Hazardous Weather Distributed Active Archive Center

    NASA Technical Reports Server (NTRS)

    Ramachandran, Rahul; Bugbee, Kaylin

    2016-01-01

    The Global Hydrology Resource Center (GHRC; ghrc.nsstc.nasa.gov) is one of NASA's twelve Distributed Active Archive Centers responsible for providing access to NASA's Earth science data to users worldwide. Each of NASA's twelve DAACs focuses on a specific science discipline within Earth science, provides data stewardship services and supports its research community's needs. Established in 1991 as the Marshall Space Flight Center DAAC and renamed GHRC in 1997, the data center's original mission focused on the global hydrologic cycle. However, over the years, data holdings, tools and expertise of GHRC have gradually shifted. In 2014, a User Working Group (UWG) was established to review GHRC capabilities and provide recommendations to make GHRC more responsive to the research community's evolving needs. The UWG recommended an update to the GHRC mission, as well as a strategic plan to move in the new direction. After a careful and detailed analysis of GHRC's capabilities, research community needs and the existing data landscape, a new mission statement for GHRC has been crafted: to provide a comprehensive active archive of both data and knowledge augmentation services with a focus on hazardous weather, its governing dynamical and physical processes, and associated applications. Within this broad mandate, GHRC will focus on lightning, tropical cyclones and storm-induced hazards through integrated collections of satellite, airborne, and in-situ data sets. The new mission was adopted at the recent 2015 UWG meeting. GHRC will retain its current name until such time as it has built substantial data holdings aligned with the new mission.

  13. Human Activity Modeling: Toward A Pragmatic Integration of Activity Theory and Usage-Centered Design

    NASA Astrophysics Data System (ADS)

    Constantine, Larry L.

    Human activity modeling is a systematic approach to organizing and representing the contextual aspects of tool use that is both well-grounded in an accepted theoretical framework and embedded within a proven design method. Activity theory provides the vocabulary and conceptual framework for understanding the human use of tools and other artifacts. Usage-centered design provides the methodological scaffolding for applying activity theory in practice. In this chapter, activity theory and usage-centered design are outlined and the connections between the two are highlighted. Simple extensions to the models of usage-centered design are introduced that together succinctly model the salient and most essential features of the activities within which tool use is embedded. Although not intended as a tutorial, examples of Activity Maps, Activity Profiles, and Participation Maps are provided.

  14. Energetics of protein fluctuations: Ligand binding to myoglobin and electron transfer in reaction center

    NASA Astrophysics Data System (ADS)

    McMahon, Benjamin Hamilton

    We have measured the temperature dependent kinetics of two different protein reactions: Psp+Qsbsp{A}{-}-> PQsb{A} electron transfer (ET) in the photosynthetic reaction (RC), and recombination of carbonmonoxide (CO) to myoglobin (Mb) after flash photolysis. The ET reaction allows determination of the temperature dependence of energy dissipation as RC adapts to charge transfer on the 100 ms, 10sp3 and 10sp4 s time scales at temperatures from 5 to 300 K. The adaptation, or conformational relaxation, of RC is observed in four distinct tiers of conformational substrates, with average apparent Arrhenius activation enthalpies of 17, 50, 78, and 110 kJ/mol and pre-exponential factors of 10sp{13},\\ 10sp{15},\\ 10sp{21}, and 10sp{25}\\ ssp{-1}, respectively. This parameterization provides a prediction of the time course of relaxations at all temperatures. At 300 K, relaxations are expected to occur from 1 ps to 1 ms; at lower temperatures the distribution of relaxation times broaden. We extend this study to samples of different pH, viscosity, and salt composition. We observe kinetics of CO recombination to horse heart myoglobin between 10 ns and 100 s at temperatures from 80 to 320 K. Essentially all recombination is visible in this time window, allowing the effect of relaxations to be observed on the nanosecond time scale at high temperatures, as well as microsecond to second time scales at lower temperatures. Variation of the solvent pH from 5.1 to 8.0 changes the average low temperature enthalpy barrier to recombination from 6 to 13 kJ/mol, shifting the time scale probed by the recombination reaction by an order of magnitude. Addition of 500 mM KCl, KSCN, or (NHsb4)sb2SOsb4 significantly changes the probability of geminate recombination without affecting either the enthalpy barrier to recombination or the energetics of CO entry to and exit from the heme pocket of the protein. We present a model of recombination which emphasizes the role of protein fluctuations in

  15. 75 FR 49946 - National Drug Intelligence Center: Agency Information Collection Activities: Proposed Extension...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-08-16

    ... National Drug Intelligence Center: Agency Information Collection Activities: Proposed Extension With Change... Response System. The United States Department of Justice (DOJ), National Drug Intelligence Center (NDIC... Intelligence Center, Fifth Floor, 319 Washington Street, Johnstown, PA 15901. Written comments and...

  16. Purification and spectroscopic characterization of photosystem II reaction center complexes isolated with or without Triton X-100.

    PubMed

    Eijckelhoff, C; van Roon, H; Groot, M L; van Grondelle, R; Dekker, J P

    1996-10-01

    The pigment composition of the isolated photosystem II reaction center complex in its most stable and pure form currently is a matter of considerable debate. In this contribution, we present a new method based on a combination of gel filtration chromatography and diode array detection to analyze the composition of photosystem II reaction center preparations. We show that the method is very sensitive for the detection of contaminants such as the core antenna protein CP47, pigment-free and denatured reaction center proteins, and unbound chlorophyll and pheophytin molecules. We also present a method by which the photosystem II reaction center complex is highly purified without using Triton X-100, and we show that in this preparation the contamination with CP47 is less than 0.1%. The results strongly indicate that the photosystem II reaction center complex in its most stable and pure form binds six chlorophyll a, two pheophytin a, and two beta-carotene molecules and that the main effect of Triton X-100 is the extraction of beta-carotene from the complex. Analysis of 4 K absorption and emission spectra indicates that the spectroscopic properties of this preparation are similar to those obtained by a short Triton X-100 treatment. In contrast, preparations obtained by long Triton X-100 treatment show decreased absorption of the shoulder at 684 nm in the 4 K absorption spectrum and an increased number of pigments that trap excitation energy at very low temperatures. We conclude that the 684 nm shoulder in the 4 K absorption spectrum should at least in part be attributed to the primary electron donor of photosystem II.

  17. [Activities of Center for Nondestructive Evaluation, Iowa State University

    NASA Technical Reports Server (NTRS)

    Gray, Joe

    2002-01-01

    The final report of NASA funded activities at Iowa State University (ISU) for the period between 1/96 and 1/99 includes two main areas of activity. The first is the development and delivery of an x-ray simulation package suitable for evaluating the impact of parameters affects the inspectability of an assembly of parts. The second area was the development of images processing tools to remove reconstruction artifacts in x-ray laminagraphy images. The x-ray simulation portion of this work was done by J. Gray and the x-ray laminagraphy work was done by J. Basart. The report is divided into two sections covering the two activities respectively. In addition to this work reported the funding also covered NASA's membership in the NSF University/Industrial Cooperative Research Center.

  18. Determination of the active center in calcium-nickel phosphate dehydrogenation catalyst

    SciTech Connect

    Attali, S.; Vigouroux, B.; Lenzi, M.; Pescia, J.

    1980-06-01

    Determination of the active center in calcium-nickel phosphate dehydrogenation catalyst, used industrially in the dehydrogenation of butenes to butadiene, showed that a stable trivalent nickel ion is involved. Apparently, electrons generated in the first (oxidation) step of the reaction are eliminated by reducing the trivalent to divalent nickel which is reoxidized by protons. The results were obtained by propanol dehydration-dehydrogenation on calcium-nickel phosphate (Ca/sub 8/Ni(PO/sub 4//sub )/6) calcined at 400/sup 0/-900/sup 0/C and by ESR spectroscopy.

  19. Architecture and evolution of Goddard Space Flight Center Distributed Active Archive Center

    NASA Technical Reports Server (NTRS)

    Bedet, Jean-Jacques; Bodden, Lee; Rosen, Wayne; Sherman, Mark; Pease, Phil

    1994-01-01

    The Goddard Space Flight Center (GSFC) Distributed Active Archive Center (DAAC) has been developed to enhance Earth Science research by improved access to remote sensor earth science data. Building and operating an archive, even one of a moderate size (a few Terabytes), is a challenging task. One of the critical components of this system is Unitree, the Hierarchical File Storage Management System. Unitree, selected two years ago as the best available solution, requires constant system administrative support. It is not always suitable as an archive and distribution data center, and has moderate performance. The Data Archive and Distribution System (DADS) software developed to monitor, manage, and automate the ingestion, archive, and distribution functions turned out to be more challenging than anticipated. Having the software and tools is not sufficient to succeed. Human interaction within the system must be fully understood to improve efficiency to improve efficiency and ensure that the right tools are developed. One of the lessons learned is that the operability, reliability, and performance aspects should be thoroughly addressed in the initial design. However, the GSFC DAAC has demonstrated that it is capable of distributing over 40 GB per day. A backup system to archive a second copy of all data ingested is under development. This backup system will be used not only for disaster recovery but will also replace the main archive when it is unavailable during maintenance or hardware replacement. The GSFC DAAC has put a strong emphasis on quality at all level of its organization. A Quality team has also been formed to identify quality issues and to propose improvements. The DAAC has conducted numerous tests to benchmark the performance of the system. These tests proved to be extremely useful in identifying bottlenecks and deficiencies in operational procedures.

  20. A full dimensional time-dependent wave packet study for the H4 four-center, collision induced dissociation, and single exchange reactions: reaction probabilities for J=0.

    PubMed

    Lu, Yunpeng; Lee, Soo-Y; Zhang, Dong H

    2006-01-07

    A time-dependent initial state selected wave packet method has been developed to study the H2(v(1)=10-11,j1=0)+H2'(v2=0,j2=0)-->HH'+HH' four-center (4C) reaction, and two other competing reactions: the H2+H2'-->H+H+H2' collision induced dissociation (CID) and the H2+H2'-->H+HH'+H' single exchange (SE) reaction, in full six dimensions. Initial state-specific total reaction probabilities for these three competing reactions are presented for total angular momentum J=0 and the effects of reagent vibration on reactions are examined. It is found that (a) the CID process is the dominant process over the whole energy range considered in this study, but the 4C and SE processes also have non-negligible probabilities; (b) the SE process has a lower threshold energy than the 4C process, but the SE probability increases slower than the 4C probability as collision energy increases; (c) the vibrational excitation of H2(v1) is much more efficient than translational motion for promoting these processes, in particular to the CID process.

  1. Structural and spectropotentiometric analysis of Blastochloris viridis heterodimer mutant reaction center

    SciTech Connect

    Ponomarenko, Nina S.; Li, Liang; Marino, Antony R.; Tereshko, Valentina; Ostafin, Agnes; Popova, Julia A.; Bylina, Edward J.; Ismagilov, Rustem F.; Norris, Jr., James R.

    2010-07-22

    Heterodimer mutant reaction centers (RCs) of Blastochloris viridis were crystallized using microfluidic technology. In this mutant, a leucine residue replaced the histidine residue which had acted as a fifth ligand to the bacteriochlorophyll (BChl) of the primary electron donor dimer M site (HisM200). With the loss of the histidine-coordinated Mg, one bacteriochlorophyll of the special pair was converted into a bacteriopheophytin (BPhe), and the primary donor became a heterodimer supermolecule. The crystals had dimensions 400 x 100 x 100 {micro}m, belonged to space group P4{sub 3}2{sub 1}2, and were isomorphous to the ones reported earlier for the wild type (WT) strain. The structure was solved to a 2.5 {angstrom} resolution limit. Electron-density maps confirmed the replacement of the histidine residue and the absence of Mg. Structural changes in the heterodimer mutant RC relative to the WT included the absence of the water molecule that is typically positioned between the M side of the primary donor and the accessory BChl, a slight shift in the position of amino acids surrounding the site of the mutation, and the rotation of the M194 phenylalanine. The cytochrome subunit was anchored similarly as in the WT and had no detectable changes in its overall position. The highly conserved tyrosine L162, located between the primary donor and the highest potential heme C{sub 380}, revealed only a minor deviation of its hydroxyl group. Concomitantly to modification of the BChl molecule, the redox potential of the heterodimer primary donor increased relative to that of the WT organism (772 mV vs. 517 mV). The availability of this heterodimer mutant and its crystal structure provides opportunities for investigating changes in light-induced electron transfer that reflect differences in redox cascades.

  2. FTIR spectroscopy of the reaction center of Chloroflexus aurantiacus: photoreduction of the bacteriopheophytin electron acceptor.

    PubMed

    Zabelin, Alexej A; Shkuropatova, Valentina A; Shuvalov, Vladimir A; Shkuropatov, Anatoly Ya

    2011-09-01

    Mid-infrared spectral changes associated with the photoreduction of the bacteriopheophytin electron acceptor H(A) in reaction centers (RCs) of the filamentous anoxygenic phototrophic bacterium Chloroflexus (Cfl.) aurantiacus are examined by light-induced Fourier transform infrared (FTIR) spectroscopy. The light-induced H(A)(-)/H(A) FTIR (1800-1200cm(-1)) difference spectrum of Cfl. aurantiacus RCs is compared to that of the previously well characterized purple bacterium Rhodobacter (Rba.) sphaeroides RCs. The most notable feature is that the large negative IR band at 1674cm(-1) in Rba. sphaeroides R-26, attributable to the loss of the absorption of the 13(1)-keto carbonyl of H(A) upon the radical anion H(A)(-) formation, exhibits only a very minor upshift to 1675cm(-1) in Cfl. aurantiacus. In contrast, the absorption band of the 13¹-keto C=O of H(A)(-) is strongly upshifted in the spectrum of Cfl. aurantiacus compared to that of Rba. sphaeroides (from 1588 to 1623cm(-1)). The data are discussed in terms of: (i) replacing the glutamic acid at L104 in Rba. sphaeroides R-26 RCs by a weaker hydrogen bond donor, a glutamine, at the equivalent position L143 in Cfl. aurantiacus RCs; (ii) a strengthening of the hydrogen-bonding interaction of the 13¹-keto C=O of H(A) with Glu L104 and Gln L143 upon H(A)(-) formation and (iii) a possible influence of the protein dielectric environment on the 13¹-keto C=O stretching frequency of neutral H(A). A conformational heterogeneity of the 13³-ester C=O group of H(A) is detected for Cfl. aurantiacus RCs similar to what has been previously described for purple bacterial RCs.

  3. Germinal Center Reaction Following Cutaneous Dengue Virus Infection in Immune-Competent Mice

    PubMed Central

    Yam-Puc, Juan Carlos; García-Cordero, Julio; Calderón-Amador, Juana; Donis-Maturano, Luis; Cedillo-Barrón, Leticia; Flores-Romo, Leopoldo

    2015-01-01

    Dengue virus (DENV) has four serotypes, which can cause from asymptomatic disease to severe dengue. Heterologous secondary infections have been associated to a greater risk of potentially fatal dengue due to non-neutralizing memory antibodies (Abs), which facilitate the infection, such as anti-precursor membrane (prM) Abs, among other mechanisms. Usually, class-switched memory Abs are generated mainly through germinal centers (GCs). However, the cellular events underlying these Ab responses to DENV, especially during repeated/secondary infections, have been poorly studied. We wanted to know whether there is involvement of GC reactions during cutaneous DENV infection and whether there is any sort of preferential Ab responses to defined viral proteins. Intradermal DENV inoculation at a relatively low dose efficiently infects immune-competent BALB/c mice, inducing higher quantities of DENV-specific GC B cells and larger GCs than the control conditions. Interestingly, GCs exhibited as much prM as envelope (E) and non-structural 3 viral proteins in situ. Intriguingly, despite the much larger abundance of E protein than of prM protein in the virions, infected animals showed similar amounts of circulating Abs and Ag-specific GC B cells both for prM and for E proteins, even significantly higher for prM. To the best of our knowledge, there are no reports of the GC responses during DENV infection. This relatively stronger anti-prM response could be triggered by DENV to preferentially promote Abs against certain viral proteins, which might favor infections by facilitating DENV invasion of host cells. It is thus conceivably that DENV might have evolved to induce this kind of Ab responses. PMID:25964784

  4. Primary charge separation and energy transfer in the photosystem I reaction center of higher plants

    SciTech Connect

    White, N.T.H.; Beddard, G.S.; Thorne J.R.G.; Feehan, T.M.; Keyes, T.E.; Heathcote, P.

    1996-07-18

    Using low intensity femtosecond duration laser pulses at 708 nm, we have observed absorption transients associated with electron transfer through the primary electron acceptor A{sub 0} in the photosystem I (PSI) reaction center from spinach under nonreducing conditions. At this wavelength the electron donor P{sub 700} is excited directly, although some antenna chlorophylls are also excited. Using a nanosecond duration preflash of 690 nm to oxidize P{sub 700}, and then measuring the absorption transients from the antenna alone, it is possible by subtraction to isolate the absorption transients arising from electron transfer. We discuss this method critically. Th spectrum of A{sub 0}{sup -}-A{sub 0} does not appear promptly but takes nearly 3 ps to reach maximum intensity and resembles those spectra previously obtained from higher plants, with a maximum bleaching at 685{+-}2 nm and a shoulder in the region 670-675 nm. The decay time of the primary radical pair P{sub 700}{sup +}A{sub 0}{sup -} is calculated as 20 ps. Analysis of absorption transients indicates that the intrinsic rate constant forming the primary radical pair P{sub 700}{sup +}A{sub 0}{sup -} cannot be measured directly because energy migration in the antenna is fast and quenching is approaching `trap limited` behavior. With use of a detailed model of the antenna energy migration based on the X-ray structure, the intrinsic rate constant for electron transfer is estimated as k{sub 1} nearly equals 0.7 ps{sup -1}. 81 refs., 15 figs., 1 tab.

  5. Calculated coupling of electron and proton transfer in the photosynthetic reaction center of Rhodopseudomonas viridis.

    PubMed Central

    Lancaster, C R; Michel, H; Honig, B; Gunner, M R

    1996-01-01

    Based on new Rhodopseudomonas (Rp.) viridis reaction center (RC) coordinates with a reliable structure of the secondary acceptor quinone (QB) site, a continuum dielectric model and finite difference technique have been used to identify clusters of electrostatically interacting ionizable residues. Twenty-three residues within a distance of 25 A from QB (QB cluster) have been shown to be strongly electrostatically coupled to QB, either directly or indirectly. An analogous cluster of 24 residues is found to interact with QA (QA cluster). Both clusters extend to the cytoplasmic surface in at least two directions. However, the QB cluster differs from the QA cluster in that it has a surplus of acidic residues, more strong electrostatic interactions, is less solvated, and experiences a strong positive electrostatic field arising from the polypeptide backbone. Consequently, upon reduction of QA or QB, it is the QB cluster, and not the QA cluster, which is responsible for substoichiometric proton uptake at neutral pH. The bulk of the changes in the QB cluster are calculated to be due to the protonation of a tightly coupled cluster of the three Glu residues (L212, H177, and M234) within the QB cluster. If the lifetime of the doubly reduced state QB2- is long enough, Asp M43 and Ser L223 are predicted to also become protonated. The calculated complex titration behavior of the strongly interacting residues of the QB cluster and the resulting electrostatic response to electron transfer may be a common feature in proton-transferring membrane protein complexes. Images FIGURE 2 p2482-a FIGURE 6 FIGURE 8 FIGURE 10 PMID:8744288

  6. Cumulant analysis of charge recombination kinetics in bacterial reaction centers reconstituted into lipid vesicles.

    PubMed Central

    Palazzo, G; Mallardi, A; Giustini, M; Berti, D; Venturoli, G

    2000-01-01

    The kinetics of charge recombination between the primary photoxidized donor (P(+)) and the secondary reduced quinone acceptor (Q(B)(-)) have been studied in reaction centers (RCs) from the purple photosynthetic bacterium Rhodobacter sphaeroides incorporated into lecithin vesicles containing large ubiquinone pools over the temperature range 275 K = (50 +/- 15) nm). Following these premises, we describe the kinetics of P(+)Q(B)(-) recombination with a truncated cumulant expansion and relate it to P(Q) and to the free energy changes for Q(A)(-)Q(B) --> Q(A)Q(B)(-) electron transfer (DeltaG(AB)(o)) and for quinone binding (DeltaG(bind)(o)) at Q(B). The model accounts well for the temperature and quinone dependence of the charge recombination kinetics, yielding DeltaG(AB)(o) = -7.67 +/- 0.05 kJ mol(-1) and DeltaG(bind)(o) = -14.6 +/- 0.6 kJ mol(-1) at 298 K. PMID:10968981

  7. Optimizing multi-step B-side charge separation in photosynthetic reaction centers from Rhodobacter capsulatus

    SciTech Connect

    Faries, Kaitlyn M.; Kressel, Lucas L.; Dylla, Nicholas P.; Wander, Marc J.; Hanson, Deborah K.; Holten, Dewey; Laible, Philip D.; Kirmaier, Christine

    2016-02-01

    Using high-throughput methods for mutagenesis, protein isolation and charge-separation functionality, we have assayed 40 Rhodobacter capsulatus reaction center (RC) mutants for their P+ QB- yield (P is a dimer of bacteriochlorophylls and Q is a ubiquinone) as produced using the normally inactive B-side cofactors BB and HB (where B is a bacteriochlorophyll and H is a bacteriopheophytin). Two sets of mutants explore all possible residues at M131 (M polypeptide, native residue Val near HB) in tandem with either a fixed His or a fixed Asn at L181 (L polypeptide, native residue Phe near BB). A third set of mutants explores all possible residues at L181 with a fixed Glu at M131 that can form a hydrogen bond to HB. For each set of mutants, the results of a rapid millisecond screening assay that probes the yield of P+ QB- are compared among that set and to the other mutants reported here or previously. For a subset of eight mutants, the rate constants and yields of the individual B-side electron transfer processes are determined via transient absorption measurements spanning 100 fs to 50 μs. The resulting ranking of mutants for their yield of P+ QB- from ultrafast experiments is in good agreement with that obtained from the millisecond screening assay, further validating the efficient, high-throughput screen for B-side transmembrane charge separation. Results from mutants that individually show progress toward optimization of P+ HB- → P+ QB- electron transfer or initial P* → P+ HB- conversion highlight unmet challenges of optimizing both processes simultaneously.

  8. [Research activities in Kobe-Indonesia Collaborative Research Centers].

    PubMed

    Utsumi, Takako; Hayashi, Yoshitake; Hotta, Hak

    2013-01-01

    Kobe-Indonesia Collaborative Research Center was established in Institute of Tropical Disease (ITD), Airlangga University, Surabaya, Indonesia in 2007 under the program of ''Founding Research Centers for Emerging and Reemerging Infectious Diseases'' supported by the Ministry of Education, Culture, Sports, Science and Technology, Japan, and then it has been under the Japan Initiative for Global Research Network on Infectious Diseases (J-GRID) since 2010. Japanese researchers have been stationed at ITD, conducting joint researches on influenza, viral hepatitis, dengue and infectious diarrhea. Also, another Japanese researcher has been stationed at Faculty of Medicine, University of Indonesia, Jakarta, carrying out joint researches on'' Identification of anti-hepatitis C virus (HCV) substances and development of HCV and dengue vaccines'' in collaboration with University of Indonesia and Airlangga University through the Science and Technology Research Partnership for Sustainable Development (SATREPS) supported by the Japan Science and Technology Agency (JST) and Japan International Cooperation Agency (JICA) since 2009. In this article, we briefly introduce the background history of Kobe University Research Center in Indonesia, and discuss the research themes and outcomes of J-GRID and SATREPS activities.

  9. Antituberculosis activity of the molecular libraries screening center network library.

    PubMed

    Maddry, Joseph A; Ananthan, Subramaniam; Goldman, Robert C; Hobrath, Judith V; Kwong, Cecil D; Maddox, Clinton; Rasmussen, Lynn; Reynolds, Robert C; Secrist, John A; Sosa, Melinda I; White, E Lucile; Zhang, Wei

    2009-09-01

    There is an urgent need for the discovery and development of new antitubercular agents that target novel biochemical pathways and treat drug-resistant forms of the disease. One approach to addressing this need is through high-throughput screening of drug-like small molecule libraries against the whole bacterium in order to identify a variety of new, active scaffolds that will stimulate additional biological research and drug discovery. Through the Molecular Libraries Screening Center Network, the NIAID Tuberculosis Antimicrobial Acquisition and Coordinating Facility tested a 215,110-compound library against Mycobacterium tuberculosis strain H37Rv. A medicinal chemistry survey of the results from the screening campaign is reported herein.

  10. A new mathematical solution for predicting char activation reactions

    USGS Publications Warehouse

    Rafsanjani, H.H.; Jamshidi, E.; Rostam-Abadi, M.

    2002-01-01

    The differential conservation equations that describe typical gas-solid reactions, such as activation of coal chars, yield a set of coupled second-order partial differential equations. The solution of these coupled equations by exact analytical methods is impossible. In addition, an approximate or exact solution only provides predictions for either reaction- or diffusion-controlling cases. A new mathematical solution, the quantize method (QM), was applied to predict the gasification rates of coal char when both chemical reaction and diffusion through the porous char are present. Carbon conversion rates predicted by the QM were in closer agreement with the experimental data than those predicted by the random pore model and the simple particle model. ?? 2002 Elsevier Science Ltd. All rights reserved.

  11. Activity Trends of Binary Silver Alloy Nanocatalysts for Oxygen Reduction Reaction in Alkaline Media.

    PubMed

    Wu, Xiaoqiang; Chen, Fuyi; Zhang, Nan; Lei, Yimin; Jin, Yachao; Qaseem, Adnan; Johnston, Roy L

    2017-02-02

    The electrocatalytic activity of Pt-based alloys exhibits a strong dependence on their electronic structures, but a relationship between electronic structure and oxygen reduction reaction (ORR) activity in Ag-based alloys is still not clear. Here, a vapor deposition based approach is reported for the preparation of Ag75 M25 (M = Cu, Co, Fe, and In) and Agx Cu100-x (x = 0, 25, 45, 50, 55, 75, 90, and 100) nanocatalysts and their electronic structures are determined by valence band spectra. The relationship of the d-band center and ORR activity exhibits volcano-shape behaviors, where the maximum catalytic activity is obtained for Ag75 Cu25 alloys. The ORR enhancement of Ag75 Cu25 alloys originates from the 0.12 eV upshift in d-band center relative to pure Ag, which is different from the downshift in the d-band center in Pt-based alloys. The activity trend for these Ag75 M25 alloys is in the order of Ag75 Cu25 > Ag75 Fe25 > Ag75 Co25 . These results provide an insight to understand the activity and stability enhancement of Ag75 Cu25 and Ag50 Cu50 catalysts by alloying.

  12. Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center

    DOE PAGES

    Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.

    2015-10-16

    A chromium(I) dinitrogen complex reacts rapidly with O2 to form the mononuclear dioxo complex [TptBu,MeCrV(O)2] (TptBu,Me=hydrotris(3-tert-butyl-5-methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [TptBu,MeCrIII(S2)]. The transformation of the putative peroxo intermediate [TptBu,MeCrIII(O2)] (S=3/2) into [TptBu,MeCrV(O)2] (S=1/2) is spin-forbidden. The minimum-energy crossing point for the two potential energy surfaces has been identified. Finally, although the dinuclear complex [(TptBu,MeCr)2(μ-O)2] exists, mechanistic experiments suggest that O2 activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface.

  13. Space weather activities at NOAA s Space Environment Center

    NASA Astrophysics Data System (ADS)

    Kunches, J.

    The NOAA Space Environment Center is the focal point for real-time space weather monitoring and prediction in the United States . The Space Weather Operations (SWO) division staffs a 24-hour/day operations center, through which both in-situ and remotely sensed data and imagery flow. These diverse data streams are analyzed continuously, and that information is applied to both predictions and specifications of various aspects of the space environment. These include the behavior of the geomagnetic field, the character of the ionosphere, and the strength of the near-earth radiation environment. Models are brought to bear in each of thes e areas, as SEC has an active research-to-operations transition effort. The Rapid Prototyping Center is the venue through which pertinent models and data must pass to be brought into the operational arena. The model outputs are then made available both internally and externally. SEC is a member of the International Space Environment Service (ISES), a partnership currently consisting of eleven nations. The mission of the ISES is to encourage and facilitate near-real-time international monitoring and prediction of the space environment by: the rapid exchange of space environment information; the standardization of the methodology for space environment observations and data reduction; the uniform publication of observations and statistics; and the application of standardized space environment products and services to assist users in reducing the impact of space weather on activities of human interest. An overview of the operational attributes of the SEC, and the function of the ISES, will be presented. Additional issues related to space weather customers, new data streams to be available in the near-term, and how these new data and imagery will be integrated int o operations will be discussed.

  14. Carbon Nanotube Activities at NASA-Johnson Space Center

    NASA Technical Reports Server (NTRS)

    Arepalli, Sivaram

    2006-01-01

    Research activities on carbon nanotubes at NASA-Johnson Space Center include production, purification, characterization and their applications for human space flight. In-situ diagnostics during nanotube production by laser oven process include collection of spatial and temporal data of passive emission and laser induced fluorescence from C2, C3 and Nickel atoms in the plume. Details of the results from the "parametric study" of the pulsed laser ablation process indicate the effect of production parameters including temperature, buffer gas, flow rate, pressure, and laser fluence. Improvement of the purity by a variety of steps in the purification process is monitored by characterization techniques including SEM, TEM, Raman, UV-VIS-NIR and TGA. A recently established NASA-JSC protocol for SWCNT characterization is undergoing revision with feedback from nanotube community. Efforts at JSC over the past five years in composites have centered on structural polymednanotube systems. Recent activities broadened this focus to multifunctional materials, supercapacitors, fuel cells, regenerable CO2 absorbers, electromagnetic shielding, radiation dosimetry and thermal management systems of interest for human space flight. Preliminary tests indicate improvement of performance in most of these applications because of the large surface area as well as high electrical and thermal conductivity exhibited by SWCNTs.

  15. Nanotube Activities at NASA-Johnson Space Center

    NASA Technical Reports Server (NTRS)

    Arepalli, Sivaram

    2004-01-01

    Nanotube activities at NASA-Johnson Space Center include production, purification, characterization as well as applications of single wall carbon nanotubes (SWCNTs). A parametric study of the pulsed laser ablation process is recently completed to monitor the effect of production parameters including temperature, buffer gas, flow rate, pressure, and laser fluence. Enhancement of production is achieved by rastering the graphite target and by increasing the target surface temperature with a cw laser. In-situ diagnostics during production included time resolved passive emission and laser induced fluorescence from the plume. The improvement of the purity by a variety of steps in the purification process is monitored by characterization techniques including SEM, TEM, Raman, UV-VIS-NIR and TGA. A recently established NASA-JSC protocol for SWCNT characterization is undergoing revision with feedback from nanotube community. Efforts at JSC over the past five years in composites have centered on structural polymer/nanotube systems. Recent activities broadened this focus to multifunctional materials, supercapacitors, fuel cells, regenerable CO2 absorbers, electromagnetic shielding, radiation dosimetry and thermal management systems of interest for human space flight. Preliminary tests indicate improvement of performance in most of these applications because of the large Surface area as well as high electrical and thermal conductivity exhibited by SWCNTs. Comparison with existing technologies and possible future improvements in the SWCNT materials sill be presented.

  16. The Land Processes Distributed Active Archive Center (LP DAAC)

    USGS Publications Warehouse

    Golon, Danielle K.

    2016-10-03

    The Land Processes Distributed Active Archive Center (LP DAAC) operates as a partnership with the U.S. Geological Survey and is 1 of 12 DAACs within the National Aeronautics and Space Administration (NASA) Earth Observing System Data and Information System (EOSDIS). The LP DAAC ingests, archives, processes, and distributes NASA Earth science remote sensing data. These data are provided to the public at no charge. Data distributed by the LP DAAC provide information about Earth’s surface from daily to yearly intervals and at 15 to 5,600 meter spatial resolution. Data provided by the LP DAAC can be used to study changes in agriculture, vegetation, ecosystems, elevation, and much more. The LP DAAC provides several ways to access, process, and interact with these data. In addition, the LP DAAC is actively archiving new datasets to provide users with a variety of data to study the Earth.

  17. Regulation of the primary quinone binding conformation by the H subunit in reaction centers from Rhodobacter sphaeroides.

    PubMed

    Sun, Chang; Taguchi, Alexander T; Beal, Nathan J; O'Malley, Patrick J; Dikanov, Sergei A; Wraight, Colin A

    2015-11-19

    Unlike photosystem II (PSII) in higher plants, bacterial photosynthetic reaction centers (bRCs) from Proteobacteria have an additional peripheral membrane subunit "H". The H subunit is necessary for photosynthetic growth, but can be removed chemically in vitro. The remaining LM dimer retains its activity to perform light-induced charge separation. Here we investigate the influence of the H subunit on interactions between the primary semiquinone and the protein matrix, using a combination of site-specific isotope labeling, pulsed electron paramagnetic resonance (EPR), and density functional theory (DFT) calculations. The data reveal substantially weaker binding interactions between the primary semiquinone and the LM dimer than observed for the intact bRC; the amount of electron spin transferred to the nitrogen hydrogen bond donors is significantly reduced, the methoxy groups are more free to rotate, and the spectra indicate a heterogeneous mixture of bound semiquinone states. These results are consistent with a loosening of the primary quinone binding pocket in the absence of the H subunit.

  18. CXCL13 is a plasma biomarker of germinal center activity

    PubMed Central

    Havenar-Daughton, Colin; Lindqvist, Madelene; Heit, Antje; Wu, Jennifer E.; Reiss, Samantha M.; Kendric, Kayla; Bélanger, Simon; Kasturi, Sudhir Pai; Landais, Elise; McGuire, Helen M.; Bothwell, Marcella; Vagefi, Parsia A.; Scully, Eileen; Tomaras, Georgia D.; Davis, Mark M.; Poignard, Pascal; Ahmed, Rafi; Walker, Bruce D.; Pulendran, Bali; McElrath, M. Juliana; Kaufmann, Daniel E.; Crotty, Shane

    2016-01-01

    Significantly higher levels of plasma CXCL13 [chemokine (C-X-C motif) ligand 13] were associated with the generation of broadly neutralizing antibodies (bnAbs) against HIV in a large longitudinal cohort of HIV-infected individuals. Germinal centers (GCs) perform the remarkable task of optimizing B-cell Ab responses. GCs are required for almost all B-cell receptor affinity maturation and will be a critical parameter to monitor if HIV bnAbs are to be induced by vaccination. However, lymphoid tissue is rarely available from immunized humans, making the monitoring of GC activity by direct assessment of GC B cells and germinal center CD4+ T follicular helper (GC Tfh) cells problematic. The CXCL13–CXCR5 [chemokine (C-X-C motif) receptor 5] chemokine axis plays a central role in organizing both B-cell follicles and GCs. Because GC Tfh cells can produce CXCL13, we explored the potential use of CXCL13 as a blood biomarker to indicate GC activity. In a series of studies, we found that plasma CXCL13 levels correlated with GC activity in draining lymph nodes of immunized mice, immunized macaques, and HIV-infected humans. Furthermore, plasma CXCL13 levels in immunized humans correlated with the magnitude of Ab responses and the frequency of ICOS+ (inducible T-cell costimulator) Tfh-like cells in blood. Together, these findings support the potential use of CXCL13 as a plasma biomarker of GC activity in human vaccine trials and other clinical settings. PMID:26908875

  19. Personality Factors Associated with the Predicted Role of Activity-Centered Versus Textbook-Centered Preservice Elementary Science Teachers

    ERIC Educational Resources Information Center

    Taylor, L. Eldon; Armstrong, Terry R.

    1975-01-01

    Describes a study in which the Predicted Role Measure (PRM) was found to be a predictive instrument for separating preservice teachers into activity-centered and textbook-centered elementary science teachers. Using Cattell's 16-Personality Factor Questionnaire, a significant difference was also found between the personality profiles of the two…

  20. Vibrational coherence in bacterial reaction centers with genetically modified B-branch pigment composition.

    PubMed

    Yakovlev, Andrei G; Shkuropatova, Tatiana A; Vasilieva, Luidmila G; Shkuropatov, Anatoli Ya; Gast, Peter; Shuvalov, Vladimir A

    2006-01-01

    Femtosecond absorption difference spectroscopy was applied to study the time and spectral evolution of low-temperature (90 K) absorbance changes in isolated reaction centers (RCs) of the HM182L mutant of Rhodobacter (Rb.) sphaeroides. In this mutant, the composition of the B-branch RC cofactors is modified with respect to that of wild-type RCs by replacing the photochemically inactive BB accessory bacteriochlorophyll (BChl) by a photoreducible bacteriopheophytin molecule (referred to as PhiB). We have examined vibrational coherence within the first 400 fs after excitation of the primary electron donor P with 20-fs pulses at 870 nm by studying the kinetics of absorbance changes at 785 nm (PhiB absorption band), 940 nm (P*-stimulated emission), and 1020 nm (BA- absorption band). The results of the femtosecond measurements are compared with those recently reported for native Rb. sphaeroides R-26 RCs containing an intact BB BChl. At delay times longer than approximately 50 fs (maximum at 120 fs), the mutant RCs exhibit a pronounced BChl radical anion (BA-) absorption band at 1020 nm, which is similar to that observed for Rb. sphaeroides R-26 RCs and represents the formation of the intermediate charge-separated state P+ BA-. Femtosecond oscillations are revealed in the kinetics of the absorption development at 1020 nm and of decay of the P*-stimulated emission at 940 nm, with the oscillatory components of both kinetics displaying a generally synchronous behavior. These data are interpreted in terms of coupling of wave packet-like nuclear motions on the potential energy surface of the P* excited state to the primary electron-transfer reaction P*-->P+ BA- in the A-branch of the RC cofactors. At very early delay times (up to 80 fs), the mutant RCs exhibit a weak absorption decrease around 785 nm that is not observed for Rb. sphaeroides R-26 RCs and can be assigned to a transient bleaching of the Qy ground-state absorption band of the PhiB molecule. In the range of 740

  1. Stigmatellin probes the electrostatic potential in the QB site of the photosynthetic reaction center.

    PubMed

    Gerencsér, László; Boros, Bogáta; Derrien, Valerie; Hanson, Deborah K; Wraight, Colin A; Sebban, Pierre; Maróti, Péter

    2015-01-20

    The electrostatic potential in the secondary quinone (QB) binding site of the reaction center (RC) of the photosynthetic bacterium Rhodobacter sphaeroides determines the rate and free energy change (driving force) of electron transfer to QB. It is controlled by the ionization states of residues in a strongly interacting cluster around the QB site. Reduction of the QB induces change of the ionization states of residues and binding of protons from the bulk. Stigmatellin, an inhibitor of the mitochondrial and photosynthetic respiratory chain, has been proven to be a unique voltage probe of the QB binding pocket. It binds to the QB site with high affinity, and the pK value of its phenolic group monitors the local electrostatic potential with high sensitivity. Investigations with different types of detergent as a model system of isolated RC revealed that the pK of stigmatellin was controlled overwhelmingly by electrostatic and slightly by hydrophobic interactions. Measurements showed a high pK value (>11) of stigmatellin in the QB pocket of the dark-state wild-type RC, indicating substantial negative potential. When the local electrostatics of the QB site was modulated by a single mutation, L213Asp → Ala, or double mutations, L213Asp-L212Glu → Ala-Ala (AA), the pK of stigmatellin dropped to 7.5 and 7.4, respectively, which corresponds to a >210 mV increase in the electrostatic potential relative to the wild-type RC. This significant pK drop (ΔpK > 3.5) decreased dramatically to (ΔpK > 0.75) in the RC of the compensatory mutant (AA+M44Asn → AA+M44Asp). Our results indicate that the L213Asp is the most important actor in the control of the electrostatic potential in the QB site of the dark-state wild-type RC, in good accordance with conclusions of former studies using theoretical calculations or light-induced charge recombination assay.

  2. Development of Secondary Archive System at Goddard Space Flight Center Version 0 Distributed Active Archive Center

    NASA Technical Reports Server (NTRS)

    Sherman, Mark; Kodis, John; Bedet, Jean-Jacques; Wacker, Chris; Woytek, Joanne; Lynnes, Chris

    1996-01-01

    The Goddard Space Flight Center (GSFC) version 0 Distributed Active Archive Center (DAAC) has been developed to support existing and pre Earth Observing System (EOS) Earth science datasets, facilitate the scientific research, and test EOS data and information system (EOSDIS) concepts. To ensure that no data is ever lost, each product received at GSFC DAAC is archived on two different media, VHS and digital linear tape (DLT). The first copy is made on VHS tape and is under the control of UniTree. The second and third copies are made to DLT and VHS media under a custom built software package named 'Archer'. While Archer provides only a subset of the functions available with commercial software like UniTree, it supports migration between near-line and off-line media and offers much greater performance and flexibility to satisfy the specific needs of a data center. Archer is specifically designed to maximize total system throughput, rather than focusing on the turn-around time for individual files. The commercial off the shelf software (COTS) hierarchical storage management (HSM) products evaluated were mainly concerned with transparent, interactive, file access to the end-user, rather than a batch-orientated, optimizable (based on known data file characteristics) data archive and retrieval system. This is critical to the distribution requirements of the GSFC DAAC where orders for 5000 or more files at a time are received. Archer has the ability to queue many thousands of file requests and to sort these requests into internal processing schedules that optimize overall throughput. Specifically, mount and dismount, tape load and unload cycles, and tape motion are minimized. This feature did not seem to be available in many COTS pacages. Archer also uses a generic tar tape format that allows tapes to be read by many different systems rather than the proprietary format found in most COTS packages. This paper discusses some of the specific requirements at GSFC DAAC, the

  3. Growing up Active: A Study into Physical Activity in Long Day Care Centers

    ERIC Educational Resources Information Center

    Cashmore, Aaron W.; Jones, Sandra C.

    2008-01-01

    The child care center is an ideal setting in which to implement strategies to promote physical activity and healthy weight, but there is a paucity of empirical evidence on factors that influence physical activity in these settings. The current study gathered initial qualitative data to explore these factors. Child care workers from five long day…

  4. Isolation of a photosystem II reaction center consisting of D-1 and D-2 polypeptides and cytochrome b-559

    SciTech Connect

    Nanba, O.; Satoh, K.

    1987-01-01

    A photosystem II reaction center complex consisting of D-1 and D-2 polypeptides and cytochrome b-559 was isolated from spinach grana thylakoids, treated with 4% (wt/vol) Triton X-100, by ion-exchange chromatography using DEAE-Toyopearl 650S. The isolated complex appears to contain five chlorophyll a, two pheophytin a, one ..beta..-carotene, and one or two cytochrome b-559 heme(s) (molar ratio) and exhibits a reversible absorbance change attributable to the photochemical accumulation of reduced pheophytin typical for the intermediary electron acceptor of photosystem II reaction center. These results strongly suggest that the site of primary charge separation in photosystem II is located on the heterodimer composed of D-1 and D-2 subunits.

  5. Center of mass detection via an active pixel sensor

    NASA Technical Reports Server (NTRS)

    Yadid-Pecht, Orly (Inventor); Minch, Brad (Inventor); Pain, Bedabrara (Inventor); Fossum, Eric (Inventor)

    2006-01-01

    An imaging system for identifying the location of the center of mass (COM) in an image. In one aspect, an imaging system includes a plurality of photosensitive elements arranged in a matrix. A center of mass circuit coupled to the photosensitive elements includes a resistive network and a normalization circuit including at least one bipolar transistor. The center of mass circuit identifies a center of mass location in the matrix and includes: a row circuit, where the row circuit identifies a center of mass row value in each row of the matrix and identifies a row intensity for each row; a horizontal circuit, where the horizontal circuit identifies a center of mass horizontal value; and a vertical circuit, where the vertical circuit identifies a center of mass vertical value. The horizontal and vertical center of mass values indicate the coordinates of the center of mass location for the image.

  6. Center of mass detection via an active pixel sensor

    NASA Technical Reports Server (NTRS)

    Yadid-Pecht, Orly (Inventor); Minch, Brad (Inventor); Pain, Bedabrata (Inventor); Fossum, Eric (Inventor)

    2005-01-01

    An imaging system for identifying the location of the center of mass (COM) in an image. In one aspect, an imaging system includes a plurality of photosensitive elements arranged in a matrix. A center of mass circuit coupled to the photosensitive elements includes a resistive network and a normalization circuit including at least one bipolar transistor. The center of mass circuit identifies a center of mass location in the matrix and includes: a row circuit, where the row circuit identifies a center of mass row value in each row of the matrix and identifies a row intensity for each row; a horizontal circuit, where the horizontal circuit identifies a center of mass horizontal value; and a vertical circuit, where the vertical circuit identifies a center of mass vertical value. The horizontal and vertical center of mass values indicate the coordinates of the center of mass location for the image.

  7. Center of mass detection via an active pixel sensor

    NASA Technical Reports Server (NTRS)

    Yadid-Pecht, Orly (Inventor); Minch, Brad (Inventor); Pain, Bedabrata (Inventor); Fossum, Eric (Inventor)

    2002-01-01

    An imaging system for identifying the location of the center of mass (COM) in an image. In one aspect, an imaging system includes a plurality of photosensitive elements arranged in a matrix. A center of mass circuit coupled to the photosensitive elements includes a resistive network and a normalization circuit including at least one bipolar transistor. The center of mass circuit identifies a center of mass location in the matrix and includes: a row circuit, where the row circuit identifies a center of mass row value in each row of the matrix and identifies a row intensity for each row; a horizontal circuit, where the horizontal circuit identifies a center of mass horizontal value; and a vertical circuit, where the vertical circuit identifies a center of mass vertical value. The horizontal and vertical center of mass values indicate the coordinates of the center of mass location for the image.

  8. Axially assembled photosynthetic reaction center mimics composed of tetrathiafulvalene, aluminum(iii) porphyrin and fullerene entities

    NASA Astrophysics Data System (ADS)

    Poddutoori, Prashanth K.; Lim, Gary N.; Sandanayaka, Atula S. D.; Karr, Paul A.; Ito, Osamu; D'Souza, Francis; Pilkington, Melanie; van der Est, Art

    2015-07-01

    The distance dependence of sequential electron transfer has been studied in six, vertical, linear supramolecular triads, (TTF-Phn-py --> AlPor-Phm-C60, n = 0, 1 and m = 1, 2, 3), constructed using tetrathiafulvalene (TTF), aluminum(iii) porphyrin (AlPor) and fullerene (C60) entities. The C60 and TTF units are bound to the Al center on opposite faces of the porphyrin; the C60 through a covalent axial bond using a benzoate spacer, and the TTF through a coordination bond via an appended pyridine. Time-resolved optical and EPR spectroscopic methods and computational studies are used to demonstrate that excitation of the porphyrin leads to step-wise, sequential electron transfer (ET) between TTF and C60, and to study the electron transfer rates and exchange coupling between the components of the triads as a function of the bridge lengths. Femtosecond transient absorption studies show that the rates of charge separation, kCS are in the range of 109-1011 s-1, depending on the length of the bridges. The lifetimes of the charge-separated state TTF&z.rad;+-C&z.rad;-60 obtained from transient absorbance experiments and the singlet lifetimes of the radical pairs obtained by time-resolved EPR are in good agreement with each other and range from 60-130 ns in the triads. The time-resolved EPR data also show that population of the triplet sublevels of the charge-separated state in the presence of a magnetic field leads to much longer lifetimes of >1 μs. The data show that a modest stabilization of the charge separation lifetime occurs in the triads. The attenuation factor β = 0.36 Å-1 obtained from the exchange coupling values between TTF&z.rad;+ and C&z.rad;-60 is consistent with values reported in the literature for oligophenylene bridged TTF-C60 conjugates. The singlet charge recombination lifetime shows a much weaker dependence on the distance between the donor and acceptor, suggesting that a simple superexchange model is not sufficient to describe the back reaction

  9. Trichloramine Removal with Activated Carbon Is Governed by Two Reductive Reactions: A Theoretical Approach with Diffusion-Reaction Models.

    PubMed

    Matsushita, Taku; Matsui, Yoshihiko; Ikekame, Shohei; Sakuma, Miki; Shirasaki, Nobutaka

    2017-04-06

    Mechanisms underlying trichloramine removal with activated carbon treatment were proven by batch experiments and theoretical analysis with diffusion-reaction models. The observed values of trichloramine and free chlorine were explained only by the model in which (1) both trichloramine and free chlorine were involved as reactants, (2) the removals of reactants were affected both by the intraparticle diffusion and by the reaction with activated carbon, and (3) trichloramine decomposition was governed by two distinct reductive reactions. One reductive reaction was expressed as a first-order reaction: the reductive reaction of trichloramine with the basal plane of PAC, which consists of graphene sheets. The other reaction was expressed as a second-order reaction: the reductive reaction of trichloramine with active functional groups located on the edge of the basal plane. Free chlorine competitively reacted with both the basal plane and the active functional groups. The fact that the model prediction succeeded even in experiments with different activated carbon doses, with different initial trichloramine concentrations, and with different sizes of activated carbon particles clearly proved that the mechanisms described in the model were reasonable for explaining trichloramine removal with activated carbon treatment.

  10. Functional capacities of human IgM memory B cells in early inflammatory responses and secondary germinal center reactions.

    PubMed

    Seifert, Marc; Przekopowitz, Martina; Taudien, Sarah; Lollies, Anna; Ronge, Viola; Drees, Britta; Lindemann, Monika; Hillen, Uwe; Engler, Harald; Singer, Bernhard B; Küppers, Ralf

    2015-02-10

    The generation and functions of human peripheral blood (PB) IgM(+)IgD(+)CD27(+) B lymphocytes with somatically mutated IgV genes are controversially discussed. We determined their differential gene expression to naive B cells and to IgM-only and IgG(+) memory B cells. This analysis revealed a high similarity of IgM(+)(IgD(+))CD27(+) and IgG(+) memory B cells but also pointed at distinct functional capacities of both subsets. In vitro analyses revealed a tendency of activated IgM(+)IgD(+)CD27(+) B cells to migrate to B-cell follicles and undergo germinal center (GC) B-cell differentiation, whereas activated IgG(+) memory B cells preferentially showed a plasma cell (PC) fate. This observation was supported by reverse regulation of B-cell lymphoma 6 and PR domain containing 1 and differential BTB and CNC homology 1, basic leucine zipper transcription factor 2 expression. Moreover, IgM(+)IgD(+)CD27(+) B lymphocytes preferentially responded to neutrophil-derived cytokines. Costimulation with catecholamines, carcinoembryonic antigen cell adhesion molecule 8 (CEACAM8), and IFN-γ caused differentiation of IgM(+)IgD(+)CD27(+) B cells into PCs, induced class switching to IgG2, and was reproducible in cocultures with neutrophils. In conclusion, this study substantiates memory B-cell characteristics of human IgM(+)IgD(+)CD27(+) B cells in that they share typical memory B-cell transcription patterns with IgG(+) post-GC B cells and show a faster and more vigorous restimulation potential, a hallmark of immune memory. Moreover, this work reveals a functional plasticity of human IgM memory B cells by showing their propensity to undergo secondary GC reactions upon reactivation, but also by their special role in early inflammation via interaction with immunomodulatory neutrophils.

  11. Selective molecular recognition, C-H bond activation, and catalysis in nanoscale reaction vessels

    SciTech Connect

    Fiedler, Dorothea; Leung, Dennis H.; Raymond, Kenneth N.; Bergman, Robert G.

    2004-11-27

    Supramolecular chemistry represents a way to mimic enzyme reactivity by using specially designed container molecules. We have shown that a chiral self-assembled M{sub 4}L{sub 6} supramolecular tetrahedron can encapsulate a variety of cationic guests, with varying degrees of stereoselectivity. Reactive iridium guests can be encapsulated and the C-H bond activation of aldehydes occurs, with the host cavity controlling the ability of substrates to interact with the metal center based upon size and shape. In addition, the host container can act as a catalyst by itself. By restricting reaction space and preorganizing the substrates into reactive conformations, it accelerates the sigmatropic rearrangement of enammonium cations.

  12. Center-of-pressure movements during equine-assisted activities.

    PubMed

    Clayton, Hilary M; Kaiser, Leeann J; de Pue, Bonnie; Kaiser, Lana

    2011-01-01

    We compared anteroposterior and mediolateral range of motion and velocity of the center of pressure (COP) on the horse's back between riders without disabilities and riders with cerebral palsy. An electronic pressure mat was used to track COP movements beneath the saddle in 4 riders without disabilities and 4 riders with cerebral palsy. Comparisons between rider groups were made using the Mann-Whitney test (p < .05). The two rider groups differed significantly in anteroposterior range of COP motion, mediolateral range of COP motion, and mediolateral COP velocity. Anteroposterior COP velocity did not differ between groups. The results suggest that measurements of COP range of motion and velocity are potentially useful for monitoring changes in balance as an indicator of core stability during equine-assisted activities.

  13. Antituberculosis Activity of the Molecular Libraries Screening Center Network Library

    PubMed Central

    MADDRY, JOSEPH A.; ANANTHAN, SUBRAMANIAM; GOLDMAN, ROBERT C.; HOBRATH, JUDITH V.; KWONG, CECIL D.; MADDOX, CLINTON; RASMUSSEN, LYNN; REYNOLDS, ROBERT C.; SECRIST, JOHN A.; SOSA, MELINDA I.; WHITE, E. LUCILE; ZHANG, WEI

    2009-01-01

    SUMMARY There is an urgent need for the discovery and development of new antitubercular agents that target novel biochemical pathways and treat drug-resistant forms of the disease. One approach to addressing this need is through high-throughput screening of drug-like small molecule libraries against the whole bacterium in order to identify a variety of new, active scaffolds that will stimulate additional biological research and drug discovery. Through the Molecular Libraries Screening Center Network, the NIAID Tuberculosis Antimicrobial Acquisition and Coordinating Facility tested a 215,110-compound library against M. tuberculosis strain H37Rv. A medicinal chemistry survey of the results from the screening campaign is reported herein. PMID:19783214

  14. Infrared spectroelectrochemistry of bacteriochlorophylls and bacteriopheophytins: Implications for the binding of the pigments in the reaction center from photosynthetic bacteria.

    PubMed

    Mäntele, W G; Wollenweber, A M; Nabedryk, E; Breton, J

    1988-11-01

    The IR spectra of the bacteriochlorophyll a and b cations and the bacteriopheophytin a and b anions were obtained by using an IR and optically transparent electrochemical cell. Prominent effects of radical formation on the vibrational spectra were found for bands assigned to the ester, keto, and acetyl C=O groups and for vibrations from macrocycle bonds. The (radical-minus-neutral) difference spectra are compared to the light-induced difference spectra of the primary donor photooxidation and the intermediary acceptor photoreduction in the reaction center of photosynthetic bacteria. Light-induced absorbance changes from bacteriochlorophyll a-containing reaction centers bear striking similarities to the electrochemically induced absorbance changes observed upon formation of bacteriochlorophyll a(+)in vitro. Comparison of the radical formation in vitro in a hydrogen-bonding or a nonhydrogen-bonding solvent suggests an ester C=O group hydrogen bonded in the neutral state but free in the cation state. For the keto C=O group, the same comparison indicates one free carbonyl group. The (anion-minus-neutral) difference spectra of bacteriopheophytin a and b exhibit a single band in the ester C=O frequency range. In contrast, two bands are observed in the difference spectra of the intermediary acceptor reduction in the reaction center of Rhodopseudomonas viridis. The higher frequency band exhibits a sensitivity to (1)H-(2)H exchange, which suggests a contribution from a protonated carboxyl group of an amino acid side chain.

  15. Coupling of cytochrome and quinone turnovers in the photocycle of reaction centers from the photosynthetic bacterium Rhodobacter sphaeroides.

    PubMed Central

    Osváth, S; Maróti, P

    1997-01-01

    A minimal kinetic model of the photocycle, including both quinone (Q-6) reduction at the secondary quinone-binding site and (mammalian) cytochrome c oxidation at the cytochrome docking site of isolated reaction centers from photosynthetic purple bacteria Rhodobacter sphaeroides, was elaborated and tested by cytochrome photooxidation under strong continuous illumination. The typical rate of photochemical excitation by a laser diode at 810 nm was 2.200 s-1, and the rates of stationary turnover of the reaction center (one-half of that of cytochrome photooxidation) were 600 +/- 70 s-1 at pH 6 and 400 +/- 50 s-1 at pH 8. The rate of turnover showed strong pH dependence, indicating the contribution of different rate-limiting processes. The kinetic limitation of the photocycle was attributed to the turnover of the cytochrome c binding site (pH < 6), light intensity and quinone/quinol exchange (6 < pH < 8), and proton-coupled second electron transfer in the quinone acceptor complex (pH > 8). The analysis of the double-reciprocal plot of the rate of turnover versus light intensity has proved useful in determining the light-independent (maximum) turnover rate of the reaction center (445 +/- 50 s-1 at pH 7.8). PMID:9251814

  16. A new photosystem II reaction center component (4.8 kDa protein) encoded by chloroplast genome.

    PubMed

    Ikeuchi, M; Inoue, Y

    1988-12-05

    The photosystem II reaction center complex, so-called D1-D2-cytochrome b-559 complex, isolated from higher plants contains a new component of about 4.8 kDa [(1988) Plant Cell Physiol. 29, 1233-1239]. The partial amino acid sequence of this component from spinach was determined after release of N-terminal blockage. The determined sequence matched an open reading frame (ORF36) of the chloroplast genome from tobacco and liverwort, which is located downstream from the psbK gene and forms an operon with psbK. The predicted product consists of 36 amino acid residues and has a single membrane-spanning segment. High homology between the tobacco and liverwort genes, and its presence in the reaction center complex suggest an important role for this component in the photosystem II complex. Since this gene corresponds to a part of the formerly designated psbI gene, we propose to revise the definition of psbI as the gene encoding the 4.8 kDa reaction center component.

  17. Determination of the primary charge separation rate in isolated photosystem II reaction centers with 500-fs time resolution

    SciTech Connect

    Wasielewski, M.R.; Johnson, D.G. ); Seibert, M. ); Govindjee )

    1989-01-01

    The authors have measured directly the rate of formation of the oxidized chlorophyll a electron donor (P680+) and the reduced electron acceptor pheophytin a{sup {minus}} (Pheoa{sup {minus}}) following excitation of isolated spinach photosystem II reaction centers at 4{degree}C. The reaction-center complex consists of D{sub 1}, D{sub 2}, and cytochrome b-559 proteins and was prepared by a procedure that stabilizes the protein complex. Transient absorption difference spectra were measured from 440 to 850 nm as a function of time with 500-fs resolution following 610-nm laser excitation. The formation of P680+-Pheoa{sup {minus}} is indicated by the appearance of a band due to P680+ at 820 nm and corresponding absorbance changes at 505 and 540 nm due to formation of Pheoa{sup {minus}}. The appearance of the 820-nm band is monoexponential with {tau} = 3.0 {plus minus} 0.6 ps. Treatment of the photosystem II reaction centers with sodium dithionite and methyl viologen followed by exposure to laser excitation, conditions known to result in accumulation of Pheoa{sup {minus}}, results in formation of a transient absorption spectrum due to {sup 1*}P680. They find no evidence for an electron acceptor that precedes the formation of Pheoa{sup {minus}}.

  18. Activity of formylphosphate in the reaction catalyzed by formyltetrahydrofolate synthetase

    SciTech Connect

    Jahansouz, H.; Kofron, J.L.; Smithers, G.W.; Himes, R.H.; Reed, G.H.

    1986-05-01

    Formylphosphate (FP), a putative enzyme-bound intermediate in the reaction catalyzed by N/sup 10/-formylH/sub 4/folate synthetase, was synthesized from formylfluoride and Pi. Measurement of hydrolysis rates by /sup 31/P NMR showed that FP is very unstable with a half-life of 48 min at 20/sup 0/C and pH 7. At pH 7 hydrolysis occurs with O-P bond cleavage as shown by /sup 18/O incorporation from /sup 18/O-H/sub 2/O into Pi. The substrate activity of FP was tested in the reaction catalyzed by N/sup 10/-formylH/sub 4/folate synthetase isolated from Clostridium cylindrosporum. MgATP + H/sub 4/folate + HCOO/sup -/ in equilibrium MgADP + Pi +N/sup 10/-formylH/sub 4/folate FP supports the reaction in both the forward and reverse directions. Thus, N/sup 10/-formylH/sub 4/folate is produced from H/sub 4/-folate and FP but only if ADP is present, and ATP is produced from FP and ADP but only if H/sub 4/folate is present. The requirements for H/sub 4/folate in the synthesis of ATP from ADP and FP and for ADP in the synthesis of N/sup 10/-formylH/sub 4/folate from FP and H/sub 4/folate, are consistent with past kinetic and isotope exchange studies which showed that the reaction proceeds by a sequential mechanism and that all three substrates must be present for any reaction to occur.

  19. Dioxygen activation at a mononuclear Cu(I) center embedded in the calix[6]arene-tren core.

    PubMed

    Izzet, Guillaume; Zeitouny, Joceline; Akdas-Killig, Huriye; Frapart, Yves; Ménage, Stéphane; Douziech, Bénédicte; Jabin, Ivan; Le Mest, Yves; Reinaud, Olivia

    2008-07-23

    The reaction of a cuprous center coordinated to a calix[6]arene-based aza-cryptand with dioxygen has been studied. In this system, Cu(I) is bound to a tren unit that caps the calixarene core at the level of the small rim. As a result, although protected from the reaction medium by the macrocycle, the metal center presents a labile site accessible to small guest ligands. Indeed, in the presence of O2, it reacts in a very fast and irreversible redox process, leading, ultimately, to Cu(II) species. In the coordinating solvent MeCN, a one electron exchange occurs, yielding the corresponding [CalixtrenCu-MeCN](2+) complex with concomitant release of superoxide in the reaction medium. In a noncoordinating solvent such as CH2Cl2, the dioxygen reaction leads to oxygen insertions into the ligand itself. Both reactions are proposed to proceed through the formation of a superoxide-Cu(II) intermediate that is unstable in the Calixtren environment due to second sphere effects. The transiently formed superoxide ligand either undergoes fast substitution for a guest ligand (in MeCN) or intramolecular redox evolutions toward oxygenation of Calixtren. Interestingly, the latter process was shown to occur twice on the same ligand, thus demonstrating a possible catalytic activation of O2 at a single cuprous center. Altogether, this study illustrates the oxidizing power of a [CuO2](+) adduct and substantiates a mechanism by which copper mono-oxygenases such as DbetaH and PHM activate O2 at the Cu(M) center to produce such an intermediate capable of C-H breaking before the electron input provided by the noncoupled Cu(H) center.

  20. Domino Michael-Michael and Aldol-Aldol Reactions: Diastereoselective Synthesis of Functionalized Cyclohexanone Derivatives Containing Quaternary Carbon Center.

    PubMed

    Ghorai, Manas K; Halder, Sandipan; Das, Subhomoy

    2015-10-02

    A simple strategy for the synthesis of highly functionalized cyclohexanone derivatives containing an all-carbon quaternary center from α-(aryl/alkyl)methylidene-β-keto esters or β-diketones via a K-enolate mediated domino Michael-Michael reaction sequence with moderate to good yield and excellent diastereoselectivity (de > 99%) is described. Interestingly, Li-base mediated reaction of α-arylmethylidene-β-diketones affords functionalized 3,5-dihydroxy cyclohexane derivatives as the kinetically controlled products via a domino aldol-aldol reaction sequence with excellent diastereoselectivity. Li-enolates of the β-keto esters or β-diketones undergo facile domino Michael-Michael reaction with nitro-olefins to afford the corresponding nitrocyclohexane derivatives in good yields and excellent diastereoselectivity (de > 99%). The formation of the products and the observed stereoselectivity were explained by plausible mechanisms and supported by extensive computational study. An asymmetric version of the protocol was explored with (L)-menthol derived nonracemic substrates, and the corresponding nonracemic cyclohexanone derivatives containing an all-carbon quaternary center were obtained with excellent stereoselectivity (de, ee > 99%).

  1. B-side electron transfer promoted by absorbance of multiple photons in Rhodobacter sphaeroides R-26 reaction centers

    SciTech Connect

    Lin, S.; Jackson, J.A.; Taguchi, A.K.W.; Woodbury, N.W.

    1999-06-03

    Femtosecond transient absorbance spectra of quinone-depleted Rhodobacter sphaeroides R-26 reaction centers in the Q{sub X} transition region have been measured at 15 K under various excitation conditions. This study focuses on the excitation wavelength dependence and excitation intensity dependence of the formation of charge-separated states on the A- and B-side of the reaction center, judging from the bleaching of the 533 nm (B-side) and 544 nm (A-side) ground-state transitions of the reaction center bacteriopheophytins (H{sub A} and H{sub B}). Upon low-intensity selective excitation directly into the bacteriopheophytin Q{sub Y} transitions (near 760 nm), bleaching of both ground-state bacteriopheophytin Q{sub X} transitions appeared immediately, showing that initially either the A- or B-side bacteriopheophytin could be excited. However, both excited states ultimately resulted in P{sup +}H{sub A}{sup {minus}} formation under these conditions. Low-intensity excitation at any of the various wavelengths showed no difference in the kinetics of the A-side charge separation forming P{sup +}H{sub A}{sup {minus}} and no substantial formation of the B-side charge-separated state, P{sup +}H{sub B}{sup {minus}}. In contrast, high-intensity 595 nm excitation resulted in substantial long-lived bleaching of the B-side bacteriopheophytin ground-state transition at 533 nm. This 533 nm bleaching was formed with essentially the same time constant as the bleaching at 544 nm due to A-side charge separation. Both bleaching bands persisted at the longest times measured in quinone-removed reaction centers. The long-lived bleaching at 533 nm using high-intensity excitation most likely represents the formation of P{sup +}H{sub B}{sup {minus}} with a relative yield of nearly 40%. One possible mechanism for B-side electron transfer is that two-photon excitation of the reaction center resulting in the state P{sup *}B{sub B}{sup *} makes P{sup +}B{sub B}{sup {minus}} thermodynamically

  2. Overview of Active Flow Control at NASA Langley Research Center

    NASA Technical Reports Server (NTRS)

    Pack, L. G.; Joslin, R. D.

    1998-01-01

    The paper summarizes Active Flow Control projects currently underway at the NASA Langley Research Center. Technology development is being pursued within a multidisciplinary, cooperative approach, involving the classical disciplines of fluid mechanics, structural mechanics, material science, acoustics, and stability and control theory. Complementing the companion papers in this session, the present paper will focus on projects that have the goal of extending the state-of-the-art in the measurement, prediction, and control of unsteady, nonlinear aerodynamics. Toward this goal, innovative actuators, micro and macro sensors, and control strategies are considered for high payoff flow control applications. The target payoffs are outlined within each section below. Validation of the approaches range from bench-top experiments to wind-tunnel experiments to flight tests. Obtaining correlations for future actuator and sensor designs are implicit in the discussion. The products of the demonstration projects and design tool development from the fundamental NASA R&D level technology will then be transferred to the Applied Research components within NASA, DOD, and US Industry. Keywords: active flow control, separation control, MEMS, review

  3. Microalloying of transition metal silicides by mechanical activation and field-activated reaction

    DOEpatents

    Munir, Zuhair A.; Woolman, Joseph N.; Petrovic, John J.

    2003-09-02

    Alloys of transition metal suicides that contain one or more alloying elements are fabricated by a two-stage process involving mechanical activation as the first stage and densification and field-activated reaction as the second stage. Mechanical activation, preferably performed by high-energy planetary milling, results in the incorporation of atoms of the alloying element(s) into the crystal lattice of the transition metal, while the densification and field-activated reaction, preferably performed by spark plasma sintering, result in the formation of the alloyed transition metal silicide. Among the many advantages of the process are its ability to accommodate materials that are incompatible in other alloying methods.

  4. Nucleotides as nucleophiles: reactions of nucleotides with phosphoimidazolide activated guanosine

    NASA Technical Reports Server (NTRS)

    Kanavarioti, A.; Rosenbach, M. T.; Hurley, T. B.

    1991-01-01

    An earlier study of the reaction of phosphoimidazolide activated nucleosides (ImpN) in aqueous phosphate buffers indicated two modes of reaction of the phosphate monoanion and dianion. The first mode is catalysis of the hydrolysis of the P-N bond in ImpN's which leads to imidazole and nucleoside 5'-monophosphate. The second represents a nucleophilic substitution of the imidazole to yield the nucleoside 5'-diphosphate. This earlier study thus served as a model for the reaction of ImpN with nucleoside monophosphates (pN) because the latter can be regarded as phosphate derivatives. In the present study we investigated the reaction of guanosine 5'-phosphate-2-methylimidazolide, 2-MeImpG, in the presence of pN (N = guanosine, adenosine and uridine) in the range 6.9 less than or equal to pH less than or equal to 7.7. We observed that pN's do act as nucleophiles to form NppG, and as general base to enhance the hydrolysis of the P-N bond in 2-MeImpG, i.e. pN show the same behavior as inorganic phosphate. The kinetic analysis yields the following rate constants for the dianion pN2-: knpN = 0.17 +/- 0.02 M-1 h-1 for nucleophilic attack and khpN = 0.11 +/- 0.07 M-1 h-1 for general base catalysis of the hydrolysis. These rate constants which are independent of the nucleobase compare with kp.2 = 0.415 M-1 h-1 and khp2. = 0.217 M-1 h-1 for the reactions of HPO4(2-). In addition, this study shows that under conditions where pN presumably form stacks, the reaction mechanism remains unchanged although in quantitative terms stacked pN are somewhat less reactive. Attack by the 2'-OH and 3'-OH groups of the ribose moiety in amounts greater than or equal to 1% is not observed; this is attributed to the large difference in nucleophilicity in the neutral pH range between the phosphate group and the ribose hydroxyls. This nucleophilicity rank is not altered by stacking.

  5. Interactions between Cytochrome c2 and the Photosynthetic Reaction Center from Rhodobacter sphaeroides : The Cation-pi Interaction†

    PubMed Central

    Paddock, M. L.; Weber, K. H.; Chang, C.; Okamura, M. Y.

    2008-01-01

    The cation-pi interaction between positively charged and aromatic groups is a common feature of many proteins and protein complexes. The structure of the complex between cytochrome c2 (cyt c2) and photosynthetic reaction center (RC) from Rhodobacter sphaeroides exhibits a cation-pi complex formed between Arg-C32 on cyt c2 and Tyr-M295 on the RC (Axelrod et. al (2002) J. Mol. Biol. 319, 501–515). The importance of the cation-pi interaction for binding and electron transfer was studied by mutating Tyr-M295 and Arg-C32. The first and second order rates for electron transfer were not affected by mutating Tyr-M295 to Ala indicating that the cation-pi complex does not greatly affect the association process or structure of the state active in electron transfer. The dissociation constant KD showed a greater increase when Try-M295 was replaced by non-aromatic Ala (3-fold) than by aromatic Phe (1.2-fold) characteristic of a cation-pi interaction. Replacement of Arg-C32 by Ala increased KD (80-fold) largely due to removal of electrostatic interactions with negatively charged residues on the RC. Replacement by Lys, increased KD (6-fold) indicating that Lys does not form a cation-pi complex. This specificity for Arg may be due to a solvation effect. Double mutant analysis indicates interaction energy between Tyr-M295 and Arg-C32 of about −24 meV (−0.6 kcal/mole). This energy is surprisingly small considering the widespread occurrence of cation-pi complexes and may be due to the trade-off between the favorable cation-pi binding energy and the unfavorable desolvation energy needed to bury Arg-C32 in the short-range contact region between the two proteins. PMID:16008347

  6. Taste-active maillard reaction products: the "tasty" world of nonvolatile maillard reaction products.

    PubMed

    Hofmann, Thomas

    2005-06-01

    This study was done to obtain greater insight into the structures and sensory activities of those tastants that are not present in foods per se, but are generated during food processing by Maillard-type reactions from carbohydrates and amino acids and thus remain unknown. In order to rank the tastants according to their relative taste impact and to identify the key tastants generated during thermal food processing, the so-called taste dilution analysis (TDA), which uses the human tongue as a biosensor for tastants, was applied to heated, intensely bitter tasting binary mixtures of glucose or xylose and proline or alanine, respectively. This screening technique led to the identification of previously unknown taste compounds, among which intensely bitter tastants such as quinizolate and homoquinizolate, a pungent-tasting pyranopyranone, cyclopentenone derivatives exhibiting a physiological cooling effect, as well as a taste-enhancing pyridinium betaine named alapyridaine will be presented.

  7. Europium (II)-doped microporous zeolite derivatives with enhanced photoluminescence by isolating active luminescence centers.

    PubMed

    Yang, Xuyong; Tiam, Tan Swee; Yu, Xibin; Demir, Hilmi Volkan; Sun, Xiao Wei

    2011-11-01

    Solid-state reaction is the most common method for preparing luminescent materials. However, the luminescent dopants in the hosts tend to aggregate in the high-temperature annealing process, which causes adverse effect in photoluminescence. Herein, we report a novel europium (II)-doped zeolite derivative prepared by a combined ion-exchange and solid-state reaction method, in which the europium (II) ions are isolated to a large extent by the micropores of the zeolite. Excited by a broad ultraviolet band from 250 to 420 nm, a strong blue emission peaking at 450 nm was observed for these Eu-embedded zeolites annealed at 800 °C in a reducing atmosphere. The zeolite host with pores of molecular dimension was found to be an excellent host to isolate and stabilize the Eu(2+) ions. The as-obtained europium (II)-doped zeolite derivative showed an approximately 9 fold enhancement in blue emission compared to that of the general europium (II)-doped aluminosilicates obtained by conventional solid-state reaction, indicating that, by isolating active luminescence centers, it is promising to achieve highly luminescent materials. Also, the strong blue emission with broad UV excitation band suggests a potential candidate of phosphor for ultraviolet excited light-emitting diode.

  8. 77 FR 69604 - Agency Information Collection Activities; Comment Request; Educational Opportunity Centers...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-11-20

    ... Agency Information Collection Activities; Comment Request; Educational Opportunity Centers Program (EOC) Annual Performance Report AGENCY: Department of Education (ED), Office of Postsecondary Education (OPE... Opportunity Centers Program (EOC) Annual Performance Report. OMB Control Number: Pending. Type of Review:...

  9. 77 FR 20887 - Proposed Information Collection (National Acquisition Center Customer Response Survey) Activity...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-04-06

    ... solicits comments on the information needed to measure customer satisfaction with delivered products and... AFFAIRS Proposed Information Collection (National Acquisition Center Customer Response Survey) Activity...: Department of Veterans Affairs (VA) National Acquisition Center Customer Response Survey, VA Form 0863....

  10. [Requests for active euthanasia: which reality in an oncology center.].

    PubMed

    Chvetzoff, G; Perret, M; Thevenet, G; Arbiol, E; Gobet, S; Saltel, P

    2009-09-01

    Euthanasia is a controversial issue in today's society. In countries where euthanasia is legal, it is mainly associated with people with cancer. We retrospectively studied the frequency and basis of patients' requests for active euthanasia in the oncology setting.MethodsRecurrent requests for euthanasia made by the patients of Leon-Berard cancer center (Lyon, France) between 2001 and 2003 were recorded by questioning the physicians and nurse supervisors in charge or by collecting information from the minutes of multidisciplinary palliative care meetings. We also collected information on the general health status of the patients, their motives and their evolution over time, as well as responses from caregivers.ResultsWe identified 16 requests for euthanasia. These involved 8 men, 7 women and 1 child (median age, 56 years), corresponding to 1% of the total deaths recorded during the period. In 2 cases, the request had come from the family only. The most frequent motives were psychological distress (38%), desire for self-autonomy (31%) and pain (31%). Half of the patients, particularly those striving for autonomy, persisted with their request until death, whereas 2 of 3 requests motivated by physical or psychological distress were not maintained. Sedation was administered to 3 patients in response to recurrent requests.ConclusionRequests for euthanasia in cancer patients are rare but may occur. Sometimes suffering is not relieved by palliative care and the request is maintained. Dealing with these patients puts caregivers in a difficult situation.

  11. Fuel Cell Activities at the NASA Glenn Research Center

    NASA Technical Reports Server (NTRS)

    Kohout, Lisa L.; Lyons, Valerie (Technical Monitor)

    2002-01-01

    Fuel cells have a long history in space applications and may have potential application in aeronautics as well. A fuel cell is an electrochemical energy conversion device that directly transforms the chemical energy of a fuel and oxidant into electrical energy. Alkaline fuel cells have been the mainstay of the U.S. space program, providing power for the Apollo missions and the Space Shuttle. However, Proton Exchange Membrane (PEM) fuel cells offer potential benefits over alkaline systems and are currently under development for the next generation Reusable Launch Vehicle (RLV). Furthermore, primary and regenerative systems utilizing PEM technology are also being considered for future space applications such as surface power and planetary aircraft. In addition to these applications, the NASA Glenn Research Center is currently studying the feasibility of the use of both PEM and solid oxide fuel cells for low- or zero-emission electric aircraft propulsion. These types of systems have potential applications for high altitude environmental aircraft, general aviation and commercial aircraft, and high attitude airships. NASA Glenn has a unique set of capabilities and expertise essential to the successful development of advanced fuel cell power systems for space and aeronautics applications. NASA Glenn's role in past fuel cell development programs as well as current activities to meet these new challenges will be presented

  12. Carbon Dioxide Information Analysis Center: FY 1991 activities

    SciTech Connect

    Cushman, R.M.; Stoss, F.W.

    1992-06-01

    During the course of a fiscal year, Oak Ridge National Laboratory`s Carbon Dioxide Information Analysis Center (CDIAC) distributes thousands of specially publications-numeric data packages (NDPs), computer model packages (CMPs), technical reports, public communication publications, newsletters, article reprints, and reference books-in response to requests for information related to global environmental issues, primarily those pertaining to climate change. CDIAC`s staff also provides technical responses to specific inquiries related to carbon dioxide (CO{sub 2}), other trace gases, and climate. Hundreds of referrals to other researchers, policy analysts, information specialists, or organizations are also facilitated by CDIAC`s staff. This report provides an account of the activities accomplished by CDIAC during the period October 1, 1990 to September 30, 1991. An organizational overview of CDIAC and its staff is supplemented by a detailed description of inquiries received and CDIAC`s response to those inquiries. An analysis and description of the preparation and distribution of numeric data packages, computer model packages, technical reports, newsletters, factsheets, specially publications, and reprints is provided. Comments and descriptions of CDIAC`s information management systems, professional networking, and special bilateral agreements are also described.

  13. Carbon Dioxide Information Analysis Center: FY 1992 activities

    SciTech Connect

    Cushman, R.M.; Stoss, F.W.

    1993-03-01

    During the course of a fiscal year, Oak Ridge National Laboratory`s Carbon Dioxide Information Analysis Center (CDIAC) distributes thousands of specialty publications-numeric data packages (NDPs), computer model packages (CMPs), technical reports, public communication publications, newsletters, article reprints, and reference books-in response to requests for information related to global environmental issues, primarily those pertaining to climate change. CDIACs staff also provides technical responses to specific inquiries related to carbon dioxide (CO{sub 2}), other trace gases, and climate. Hundreds of referrals to other researchers, policy analysts, information specialists, or organizations are also facilitated by CDIAC`s staff. This report provides an account of the activities accomplished by CDIAC during the period October 1, 1991 to September 30, 1992. An organizational overview of CDIAC and its staff is supplemented by a detailed description of inquiries received and CDIAC`s response to those inquiries. As analysis and description of the preparation and distribution of numeric data packages, computer model packages, technical reports, newsletters, fact sheets, specialty publications, and reprints is provided. Comments and descriptions of CDIAC`s information management systems, professional networking, and special bilateral agreements are also described.

  14. Carbon Dioxide Information Analysis Center: FY 1991 activities

    SciTech Connect

    Cushman, R.M.; Stoss, F.W.

    1992-06-01

    During the course of a fiscal year, Oak Ridge National Laboratory's Carbon Dioxide Information Analysis Center (CDIAC) distributes thousands of specially publications-numeric data packages (NDPs), computer model packages (CMPs), technical reports, public communication publications, newsletters, article reprints, and reference books-in response to requests for information related to global environmental issues, primarily those pertaining to climate change. CDIAC's staff also provides technical responses to specific inquiries related to carbon dioxide (CO{sub 2}), other trace gases, and climate. Hundreds of referrals to other researchers, policy analysts, information specialists, or organizations are also facilitated by CDIAC's staff. This report provides an account of the activities accomplished by CDIAC during the period October 1, 1990 to September 30, 1991. An organizational overview of CDIAC and its staff is supplemented by a detailed description of inquiries received and CDIAC's response to those inquiries. An analysis and description of the preparation and distribution of numeric data packages, computer model packages, technical reports, newsletters, factsheets, specially publications, and reprints is provided. Comments and descriptions of CDIAC's information management systems, professional networking, and special bilateral agreements are also described.

  15. Thermodynamics of electron transfer in oxygenic photosynthetic reaction centers: volume change, enthalpy, and entropy of electron-transfer reactions in manganese-depleted photosystem II core complexes.

    PubMed

    Hou, J M; Boichenko, V A; Diner, B A; Mauzerall, D

    2001-06-19

    We have previously reported the thermodynamic data of electron transfer in photosystem I using pulsed time-resolved photoacoustics [Hou et al. (2001) Biochemistry 40, 7109-7116]. In the present work, using preparations of purified manganese-depleted photosystem II (PS II) core complexes from Synechocystis sp. PCC 6803, we have measured the DeltaV, DeltaH, and estimated TDeltaS of electron transfer on the time scale of 1 micros. At pH 6.0, the volume contraction of PS II was determined to be -9 +/- 1 A3. The thermal efficiency was found to be 52 +/- 5%, which corresponds to an enthalpy change of -0.9 +/- 0.1 eV for the formation of the state P680+Q(A-) from P680*. An unexpected volume expansion on pulse saturation of PS II was observed, which is reversible in the dark. At pH 9.0, the volume contraction, the thermal efficiency, and the enthalpy change were -3.4 +/- 0.5 A3, 37 +/- 7%, and -1.15 +/- 0.13 eV, respectively. The DeltaV of PS II, smaller than that of PS I and bacterial centers, is assigned to electrostriction and analyzed using the Drude-Nernst equation. To explain the small DeltaV for the formation of P680+Q(A-) or Y(Z*)Q(A-), we propose that fast proton transfer into a polar region is involved in this reaction. Taking the free energy of charge separation of PS II as the difference between the energy of the excited-state P680* and the difference in the redox potentials of the donor and acceptor, the apparent entropy change (TDeltaS) for charge separation of PS II is calculated to be negative, -0.1 +/- 0.1 eV at pH 6.0 (P680+Q(A-)) and -0.2 +/- 0.15 eV at pH 9.0 (Y(Z*)Q(A-)). The thermodynamic properties of electron transfer in PS II core reaction centers thus differ considerably from those of bacterial and PS I reaction centers, which have DeltaV of approximately -27 A3, DeltaH of approximately -0.4 eV, and TDeltaS of approximately +0.4 eV.

  16. Porous platinum mesoflowers with enhanced activity for methanol oxidation reaction

    SciTech Connect

    Zhuang Lina; Wang Wenjin; Hong Feng; Yang Shengchun; You Hongjun; Fang Jixiang; Ding Bingjun

    2012-07-15

    Porous Pt and Pt-Ag alloy mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesized using Ag mesoflowers as sacrificial template by galvanic reaction. The silver content in Pt-Ag alloys can be facilely controlled by nitric acid treatment. And the pure Pt MFs can be obtained by selective removal of silver element from Pt{sub 72}Ag{sub 28} MFs electrochemically. Both Pt{sub 45}Ag{sub 55}, Pt{sub 72}Ag{sub 28} and pure Pt show a high catalytic performance in methanol oxidation reaction (MOR). Especially, pure Pt MFs exhibited a 2 to 3 times current density enhancement in MOR compared with the commercial used Pt black, which can be attributed to their porous nanostructure with 3-dimentional nature and small crystal sizes. - Graphical Abstract: The CVs of MOR on Pt (red) and Pt black (green) catalysts in 0.1 M HClO{sub 4} and 0.5 M CH{sub 3}OH for specific mass current. The insert shows the SEM images of two porous Pt MFs. Platinum mesoflowers (MFs) with about 2 {mu}m in diameter and high porosity were synthesised with Ag mesoflowers as sacrificial template by galvanic replacement. The porous Pt MFs exhibited a more than 3 times enhancement in electrocatalytic performance for methanol oxidation reaction compared the commercial used Pt black. Highlights: Black-Right-Pointing-Pointer Porous Pt and Pt-Ag mesoflowers (MFs) were synthesized using Ag MFs sacrifical template. Black-Right-Pointing-Pointer Pt MFs presents an improved catalytic activity in MOR compared with Pt black. Black-Right-Pointing-Pointer We provided a facile approach for the development of high performance Pt electrocatalysts for fuel cells.

  17. Circulating polymerase chain reaction chips utilizing multiple-membrane activation

    NASA Astrophysics Data System (ADS)

    Wang, Chih-Hao; Chen, Yi-Yu; Liao, Chia-Sheng; Hsieh, Tsung-Min; Luo, Ching-Hsing; Wu, Jiunn-Jong; Lee, Huei-Huang; Lee, Gwo-Bin

    2007-02-01

    This paper reports a new micromachined, circulating, polymerase chain reaction (PCR) chip for nucleic acid amplification. The PCR chip is comprised of a microthermal control module and a polydimethylsiloxane (PDMS)-based microfluidic control module. The microthermal control modules are formed with three individual heating and temperature-sensing sections, each modulating a specific set temperature for denaturation, annealing and extension processes, respectively. Micro-pneumatic valves and multiple-membrane activations are used to form the microfluidic control module to transport sample fluids through three reaction regions. Compared with other PCR chips, the new chip is more compact in size, requires less time for heating and cooling processes, and has the capability to randomly adjust time ratios and cycle numbers depending on the PCR process. Experimental results showed that detection genes for two pathogens, Streptococcus pyogenes (S. pyogenes, 777 bps) and Streptococcus pneumoniae (S. pneumoniae, 273 bps), can be successfully amplified using the new circulating PCR chip. The minimum number of thermal cycles to amplify the DNA-based S. pyogenes for slab gel electrophoresis is 20 cycles with an initial concentration of 42.5 pg µl-1. Experimental data also revealed that a high reproducibility up to 98% could be achieved if the initial template concentration of the S. pyogenes was higher than 4 pg µl-1. The preliminary results of the current paper were presented at the 19th IEEE International Conference on Micro Electro Mechanical Systems (IEEE MEMS 2006), Istanbul, Turkey, 22-26 January, 2006.

  18. Time-resolved X-, K-, and W-band EPR of the radical pair state P{sub 700}{sup {center_dot}-}A{sub 1}{sup {center_dot}-} of photosystem I in comparison with P{sub 865}{sup {center_dot}+}Q{sub A}{sup {center_dot}-} in bacterial reaction centers

    SciTech Connect

    Est, A. van der; Prisner, T.; Moebius, K.; Stehlik, D.; Bittl, R.; Fromme, P.; Lubitz, W.

    1997-02-20

    The spin-polarized EPR spectra at 95 GHz (W-band), 24 GHz (K-band), and 9 GHz (X-band) of the radical pair P{sub 700}{sup {center_dot}+}A{sub 1}{sup {center_dot}-} in highly purified photosystem I particles are presented. The spectra are analyzed to obtain both the magnetic parameters of the radical pair as well as the relative orientation of the two species. From the analysis, the g-tensor of A{sub 1}{sup {center_dot}-} is found to be g{sub xx} = 2.0062, g{sub yy} = 2.0051, and g{sub zz} = 2.0022, and it is shown that A{sub 1} is oriented such that the carbonyl bonds are parallel to the vector joining the centers of P{sub 700}{sup {center_dot}+} and A{sub 1}{sup {center_dot}-}. The anisotropy of the g-tensor is considerably larger than that obtained for chemically reduced phylloquinone in frozen 2-propanol solution. Possible reasons for this difference and their implications for the A{sub 1} binding site are discussed. The relative orientation of P{sub 700}{sup {center_dot}+} and A{sub 1}{sup {center_dot}-} is compared with earlier estimates obtained using less accurate g-values for A{sub 1}{sup {center_dot}-}. A comparison with the spectra of P{sub 865}{sup {center_dot}+}Q{sub A}{sup {center_dot}-} in bacterial reaction centers (bRCs) of Rhodobacter sphaeroides R-26 in which the nonheme iron has been replaced by zinc (Zn-bRCs) allows the structural and magnetic properties of the charge-separated state in the two systems to be compared. 52 refs., 5 figs., 7 tabs.

  19. Specific modulation of protein activity by using a bioorthogonal reaction.

    PubMed

    Warner, John B; Muthusamy, Anand K; Petersson, E James

    2014-11-24

    Unnatural amino acids with bioorthogonal reactive groups have the potential to provide a rapid and specific mechanism for covalently inhibiting a protein of interest. Here, we use mutagenesis to insert an unnatural amino acid containing an azide group (Z) into the target protein at positions such that a "click" reaction with an alkyne modulator (X) will alter the function of the protein. This bioorthogonally reactive pair can engender specificity of X for the Z-containing protein, even if the target is otherwise identical to another protein, allowing for rapid target validation in living cells. We demonstrate our method using inhibition of the Escherichia coli enzyme aminoacyl transferase by both active-site occlusion and allosteric mechanisms. We have termed this a "clickable magic bullet" strategy, and it should be generally applicable to studying the effects of protein inhibition, within the limits of unnatural amino acid mutagenesis.

  20. Activation of stratospheric chlorine by reactions in liquid sulphuric acid

    SciTech Connect

    Cox, R.A.; MacKenzie, A.R. ); Mueller, R.H.; Peter, Th.; Crutzen, P.J. )

    1994-06-22

    The authors discuss activation mechanisms for chlorine compounds in the stratosphere, based on laboratory measurements for the solubility and reaction rates of HOCl and HCl in H[sub 2]SO[sub 4] solutions, as found on aerosols in the stratosphere. Their interest is in the impact of the large increase in aerosol loading in the stratosphere in the winter on 1991-92 due to the Mt. Pinatubo eruption. While laboratory data is not available for the temperature range close to 190 K, they argue that should the solubility and hydrolysis rates be high enough, this excess aerosol density could have contributed a significant additional amount of reactive chlorine to the stratosphere.

  1. Innovative Strategy on Hydrogen Evolution Reaction Utilizing Activated Liquid Water

    PubMed Central

    Hwang, Bing-Joe; Chen, Hsiao-Chien; Mai, Fu-Der; Tsai, Hui-Yen; Yang, Chih-Ping; Rick, John; Liu, Yu-Chuan

    2015-01-01

    Splitting water for hydrogen production using light, or electrical energy, is the most developed ‘green technique’. For increasing efficiency in hydrogen production, currently, the most exciting and thriving strategies are focused on efficient and inexpensive catalysts. Here, we report an innovative idea for efficient hydrogen evolution reaction (HER) utilizing plasmon-activated liquid water with reduced hydrogen-bonded structure by hot electron transfer. This strategy is effective for all HERs in acidic, basic and neutral systems, photocatalytic system with a g-C3N4 (graphite carbon nitride) electrode, as well as in an inert system with an ITO (indium tin oxide) electrode. Compared to deionized water, the efficiency of HER increases by 48% based on activated water ex situ on a Pt electrode. Increase in energy efficiency from activated water is 18% at a specific current yield of −20 mA in situ on a nanoscale-granulated Au electrode. Moreover, the onset potential of −0.023 V vs RHE was very close to the thermodynamic potential of the HER (0 V). The measured current density at the corresponding overpotential for HER in an acidic system was higher than any data previously reported in the literature. This approach establishes a new vista in clean green energy production. PMID:26541371

  2. Innovative Strategy on Hydrogen Evolution Reaction Utilizing Activated Liquid Water

    NASA Astrophysics Data System (ADS)

    Hwang, Bing-Joe; Chen, Hsiao-Chien; Mai, Fu-Der; Tsai, Hui-Yen; Yang, Chih-Ping; Rick, John; Liu, Yu-Chuan

    2015-11-01

    Splitting water for hydrogen production using light, or electrical energy, is the most developed ‘green technique’. For increasing efficiency in hydrogen production, currently, the most exciting and thriving strategies are focused on efficient and inexpensive catalysts. Here, we report an innovative idea for efficient hydrogen evolution reaction (HER) utilizing plasmon-activated liquid water with reduced hydrogen-bonded structure by hot electron transfer. This strategy is effective for all HERs in acidic, basic and neutral systems, photocatalytic system with a g-C3N4 (graphite carbon nitride) electrode, as well as in an inert system with an ITO (indium tin oxide) electrode. Compared to deionized water, the efficiency of HER increases by 48% based on activated water ex situ on a Pt electrode. Increase in energy efficiency from activated water is 18% at a specific current yield of -20 mA in situ on a nanoscale-granulated Au electrode. Moreover, the onset potential of -0.023 V vs RHE was very close to the thermodynamic potential of the HER (0 V). The measured current density at the corresponding overpotential for HER in an acidic system was higher than any data previously reported in the literature. This approach establishes a new vista in clean green energy production.

  3. Spin densities from subsystem density-functional theory: Assessment and application to a photosynthetic reaction center complex model

    NASA Astrophysics Data System (ADS)

    Solovyeva, Alisa; Pavanello, Michele; Neugebauer, Johannes

    2012-05-01

    Subsystem density-functional theory (DFT) is a powerful and efficient alternative to Kohn-Sham DFT for large systems composed of several weakly interacting subunits. Here, we provide a systematic investigation of the spin-density distributions obtained in subsystem DFT calculations for radicals in explicit environments. This includes a small radical in a solvent shell, a π-stacked guanine-thymine radical cation, and a benchmark application to a model for the special pair radical cation, which is a dimer of bacteriochlorophyll pigments, from the photosynthetic reaction center of purple bacteria. We investigate the differences in the spin densities resulting from subsystem DFT and Kohn-Sham DFT calculations. In these comparisons, we focus on the problem of overdelocalization of spin densities due to the self-interaction error in DFT. It is demonstrated that subsystem DFT can reduce this problem, while it still allows to describe spin-polarization effects crossing the boundaries of the subsystems. In practical calculations of spin densities for radicals in a given environment, it may thus be a pragmatic alternative to Kohn-Sham DFT calculations. In our calculation on the special pair radical cation, we show that the coordinating histidine residues reduce the spin-density asymmetry between the two halves of this system, while inclusion of a larger binding pocket model increases this asymmetry. The unidirectional energy transfer in photosynthetic reaction centers is related to the asymmetry introduced by the protein environment.

  4. 34 CFR 426.7 - What activities does the Secretary fund under the Agriculture Action Centers?

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Agriculture Action Centers? 426.7 Section 426.7 Education Regulations of the Offices of the Department of... DEMONSTRATION PROGRAM General § 426.7 What activities does the Secretary fund under the Agriculture Action Centers? The Secretary supports model Agriculture Action Centers that provide improved access...

  5. 34 CFR 426.7 - What activities does the Secretary fund under the Agriculture Action Centers?

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Agriculture Action Centers? 426.7 Section 426.7 Education Regulations of the Offices of the Department of... DEMONSTRATION PROGRAM General § 426.7 What activities does the Secretary fund under the Agriculture Action Centers? The Secretary supports model Agriculture Action Centers that provide improved access...

  6. 34 CFR 426.7 - What activities does the Secretary fund under the Agriculture Action Centers?

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Agriculture Action Centers? 426.7 Section 426.7 Education Regulations of the Offices of the Department of... DEMONSTRATION PROGRAM General § 426.7 What activities does the Secretary fund under the Agriculture Action Centers? The Secretary supports model Agriculture Action Centers that provide improved access...

  7. 34 CFR 426.7 - What activities does the Secretary fund under the Agriculture Action Centers?

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Agriculture Action Centers? 426.7 Section 426.7 Education Regulations of the Offices of the Department of... DEMONSTRATION PROGRAM General § 426.7 What activities does the Secretary fund under the Agriculture Action Centers? The Secretary supports model Agriculture Action Centers that provide improved access...

  8. Analysis of absorption spectra of purple bacterial reaction centers in the near infrared region by higher order derivative spectroscopy.

    PubMed

    Mikhailyuk, I K; Knox, P P; Paschenko, V Z; Razjivin, A P; Lokstein, H

    2006-06-20

    Reaction centers (RCs) of purple bacteria are uniquely suited objects to study the mechanisms of the photosynthetic conversion of light energy into chemical energy. A recently introduced method of higher order derivative spectroscopy [I.K. Mikhailyuk, H. Lokstein, A.P. Razjivin, A method of spectral subband decomposition by simultaneous fitting the initial spectrum and a set of its derivatives, J. Biochem. Biophys. Methods 63 (2005) 10-23] was used to analyze the NIR absorption spectra of RC preparations from Rhodobacter (R.) sphaeroides strain 2R and Blastochloris (B.) viridis strain KH, containing bacteriochlorophyll (BChl) a and b, respectively. Q(y) bands of individual RC porphyrin components (BChls and bacteriopheophytins, BPheo) were identified. The results indicate that the upper exciton level P(y+) of the photo-active BChl dimer in RCs of R. sphaeroides has an absorption maximum of 810nm. The blue shift of a complex integral band at approximately 800nm upon oxidation of the RC is caused primarily by bleaching of P(y+), rather than by an electrochromic shift of the absorption band(s) of the monomeric BChls. Likewise, the disappearance of a band peaking at 842nm upon oxidation of RCs from B. viridis indicates that this band has to be assigned to P(y+). A blue shift of an absorption band at approximately 830nm upon oxidation of RCs of B. viridis is also essentially caused by the disappearance of P(y+), rather than by an electrochromic shift of the absorption bands of monomeric BChls. Absorption maxima of the monomeric BChls, B(B) and B(A) are at 802 and 797nm, respectively, in RCs of R. sphaeroides at room temperature. BPheo co-factors H(B) and H(A) peak at 748 and 758nm, respectively, at room temperature. For B. viridis RCs the spectral positions of H(B) and H(A) were found to be 796 and 816nm, respectively, at room temperature.

  9. Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

    NASA Astrophysics Data System (ADS)

    Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun; Liu, Baocang; Gong, Xia; Zheng, Dafang; Zhang, Jun; Wang, Qin

    2016-12-01

    The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg-1) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

  10. Activation energy of tantalum-tungsten oxide thermite reactions

    SciTech Connect

    Cervantes, Octavio G.; Munir, Zuhair A.; Kuntz, Joshua D.; Gash, Alexander E.

    2011-01-15

    The activation energy of a sol-gel (SG) derived tantalum-tungsten oxide thermite composite was determined using the Kissinger isoconversion method. The SG derived powder was consolidated using the high-pressure spark plasma sintering (HPSPS) technique at 300 and 400 C. The ignition temperatures were investigated under high heating rates (500-2000 C min{sup -1}). Such heating rates were required in order to ignite the thermite composite. Samples consolidated at 300 C exhibit an abrupt change in temperature response prior to the main ignition temperature. This change in temperature response is attributed to the crystallization of the amorphous WO{sub 3} in the SG derived Ta-WO{sub 3} thermite composite and not to a pre-ignition reaction between the constituents. Ignition temperatures for the Ta-WO{sub 3} thermite ranged from approximately 465 to 670 C. The activation energies of the SG derived Ta-WO{sub 3} thermite composite consolidated at 300 and 400 C were determined to be 38{+-} 2 kJ mol{sup -1} and 57 {+-} 2 kJ mol{sup -1}, respectively. (author)

  11. Isolation and characterization of homodimeric type-I reaction center complex from Candidatus Chloracidobacterium thermophilum, an aerobic chlorophototroph.

    PubMed

    Tsukatani, Yusuke; Romberger, Steven P; Golbeck, John H; Bryant, Donald A

    2012-02-17

    The recently discovered thermophilic acidobacterium Candidatus Chloracidobacterium thermophilum is the first aerobic chlorophototroph that has a type-I, homodimeric reaction center (RC). This organism and its type-I RCs were initially detected by the occurrence of pscA gene sequences, which encode the core subunit of the RC complex, in metagenomic sequence data derived from hot spring microbial mats. Here, we report the isolation and initial biochemical characterization of the type-I RC from Ca. C. thermophilum. After removal of chlorosomes, crude membranes were solubilized with 0.1% (w/v) n-dodecyl β-D-maltoside, and the RC complex was purified by ion-exchange chromatography. The RC complex comprised only two polypeptides: the reaction center core protein PscA and a 22-kDa carotenoid-binding protein denoted CbpC. The absorption spectrum showed a large, broad absorbance band centered at ∼483 nm from carotenoids as well as smaller Q(y) absorption bands at 672 and 812 nm from chlorophyll a and bacteriochlorophyll a, respectively. The light-induced difference spectra of whole cells, membranes, and the isolated RC showed maximal bleaching at 840 nm, which is attributed to the special pair and which we denote as P840. Making it unique among homodimeric type-I RCs, the isolated RC was photoactive in the presence of oxygen. Analyses by optical spectroscopy, chromatography, and mass spectrometry revealed that the RC complex contained 10.3 bacteriochlorophyll a(P), 6.4 chlorophyll a(PD), and 1.6 Zn-bacteriochlorophyll a(P)' molecules per P840 (12.8:8.0:2.0). The possible functions of the Zn-bacteriochlorophyll a(P)' molecules and the carotenoid-binding protein are discussed.

  12. Inter-and intraspecific variation in excited-state triplet energy transfer rates in reaction centers of photosynthetic bacteria.

    SciTech Connect

    Laible, P. D.; Morris, Z. S.; Thurnauer, M. C.; Schiffer, M.; Hanson, D. K.

    2003-08-01

    In protein-cofactor reaction center (RC) complexes of purple photosynthetic bacteria, the major role of the bound carotenoid (C) is to quench the triplet state formed on the primary electron donor (P) before its sensitization of the excited singlet state of molecular oxygen from its ground triplet state. This triplet energy is transferred from P to C via the bacteriochlorophyll monomer B{sub B}. Using time-resolved electron paramagnetic resonance (TREPR), we have examined the temperature dependence of the rates of this triplet energy transfer reaction in the RC of three wild-type species of purple nonsulfur bacteria. Species-specific differences in the rate of transfer were observed. Wild-type Rhodobacter capsulatus RCs were less efficient at the triplet transfer reaction than Rhodobacter sphaeroides RCs, but were more efficient than Rhodospirillum rubrum RCs. In addition, RCs from three mutant strains of R. capsulatus carrying substitutions of amino acids near P and B{sub B} were examined. Two of the mutant RCs showed decreased triplet transfer rates compared with wild-type RCs, whereas one of the mutant RCs demonstrated a slight increase in triplet transfer rate at low temperatures. The results show that site-specific changes within the RC of R. capsulatus can mimic interspecies differences in the rates of triplet energy transfer. This application of TREPR was instrumental in defining critical energetic and coupling factors that dictate the efficiency of this photoprotective process.

  13. STS-26 Mission Control Center (MCC) activity at JSC

    NASA Technical Reports Server (NTRS)

    1988-01-01

    A wide angle view shows flight controllers in JSC's Mission Control Center (MCC) Bldg 30 flight control room (FCR) as they listen to a presentation by STS-26 crewmembers on the fourth day of Discovery's, Orbiter Vehicle (OV) 103's, orbital mission. Flight Director James M. (Milt) Heflin (standing at center) and astronaut and spacecraft communicator (CAPCOM) G. David Low (standing at right) briefly look away from a television image of the crew on a screen in the front of the FCR. Heflin, Low, and other flight controllers listen as each member relates some inner feelings while paying tribute to the 51L Challenger crew.

  14. Harford-Cecil Supplementary Education Center: A Handbook of Activities.

    ERIC Educational Resources Information Center

    Harford-Cecil Supplementary Education Center, Havre de Grace, MD.

    The history and objectives of the Center are reviewed and its work is outlined, including programs for children with learning disabilities and for predelinquent boys and pregnant school age girls. Two cases involving speech training are presented as are descriptions of the communications consultant and resource teachers. Further information covers…

  15. Natural hazards activities of the National Geophysical Data Center

    USGS Publications Warehouse

    Lockridge, P.A.

    1985-01-01

    The National Geophysical Data Center (NGDC), a part of the National Oceanic and Atmospheric Administration, has been given the task of collecting, managing, and disseminating the great mass of inofmation produced by scientific observations of the geophysical environment. This article describes NGDC data bases that speifically relate to natural hazards. 

  16. Incidence of infusion reactions to anti-neoplastic agents in early phase clinical trials: The MD Anderson Cancer Center experience.

    PubMed

    Bupathi, Manojkumar; Hajjar, Joud; Bean, Stacie; Fu, Siqing; Hong, David; Karp, Daniel; Stephen, Bettzy; Hess, Kenneth; Meric-Bernstam, Funda; Naing, Aung

    2017-02-01

    Infusion reactions (IRs) to anti-neoplastic agents require prompt recognition and immediate treatment to avert significant complications. We conducted a retrospective review of the medical records of consecutive patients who received anti-neoplastic therapy in the outpatient treatment center of the Department of Investigational Cancer Therapeutics from January 1, 2013 to November 30, 2013. Of the 597 patients who received treatment, 9 (1.5 %) had IRs (all ≤ grade 2). The most common IRs observed on first occurrence were chills (n = 5), itching, rash, and facial flushing (n = 3 each). There were no IR-related deaths. All the IRs were reversible with appropriate symptomatic treatment and the therapy was completed after temporary cessation of infusion in 7 of the 9 patients. The infusion was stopped in 2 patients due to symptoms suggestive of IgE-mediated allergic reaction and cytokine storm. Five of the 8 patients who were re-challenged with the same therapy developed a similar reaction. However, the infusion was completed in 4 of the 5 patients after administration of intravenous diphenhydramine and/or hydrocortisone, or slowing the rate of infusion. And, subsequent cycles with the same agents were uneventful. IRs to anti-neoplastic agents are rare. Though the clinical presentations are overlapping, most IRs are not IgE-mediated allergic reactions. Appropriate premedication and slow rate of infusion facilitates uneventful administration of the anti-neoplastic agents in subsequent cycles. Further study in a larger cohort of patients to identify biomarkers of hypersensitivity is warranted.

  17. Electron transport, Photosystem-2 reaction centers and chlorophyll-protein complexes of thylakoids of drought resistant and sensitive Lupin piants.

    PubMed

    Meyer, S; de Kouchkovsky, Y

    1993-07-01

    Two genotypes ofLupinus albus L., resistant and susceptible to drought, were subjected to water deficiency for up to two weeks. Such treatment progressively lowered the leaf water content from about 85% to about 60% (water potential from -0.8 to -4.3 MPa). Light-saturation curves of the uncoupled electron transport were analyzed according to a simple kinetic model of separated or connected reversible photoreactions. It gives an extrapolated maximum rate (Vmax) and the efficiency for capturing light (Im, which is the light intensity at Vmax/2). For Photosystem 2, Vmax and, less markedly, Im, declined with increasing severity of drought treatment; the artificial donor, diphenylcarbazide, could not restore the activity. One cause of this Photosystem 2 inhibition could be the loss of active Photosystem 2 centers. Indeed, their concentration relative to chlorophyll, estimated by flash-induced reduction of dimethylquinone, was halved by a medium stress. To the extent that it was still not restored by diphenylcarbazide, the site of Photosystem 2 inactivation must have been close to the photochemical trap, after water oxidation and before or at plastoquinone pool. By relating electron transport rate to active centers instead of chlorophyll, no inhibition by drought was detected. Therefore, water stress inactivates specifically Photosystem 2, without impairing a downhill thermal step of electron transport. On the other hand, the decrease of Im suggests that antennae connected to inactive centers may transfer their excitation energy to active neighbors, which implies that antenna network remains essentially intact. Gel electrophoresis confirmed that the apoproteins of the pigment complexes were well conserved. In conclusion, the inactivation of Photosystem 2 may not be a physical loss of its centers and core antennae but probably reflects protein alterations or conformational changes. These may result from the massive decrease of lipids induced by drought (Meyer et al. 1992

  18. Predicted Role of Prospective Activity-Centered Vs. Textbook-Centered Elementary Science Teachers Correlated with 16 Personality Factors and Critical Thinking Abilities.

    ERIC Educational Resources Information Center

    Taylor, Loren Eldon

    The purpose of this study was to identify the personal characteristics of prospective activity-centered elementary science teachers. Having established a method of identifying activity-centered versus textbook-centered teachers, the investigator established two groups respectively, using scores on the Predicted Role Measure (PRM) instrument for…

  19. Two-Dimensional Electronic Spectroscopy of the Photosystem II D1D2-cyt.b559 Reaction Center Complex

    NASA Astrophysics Data System (ADS)

    Myers, Jeffrey Allen

    Two-dimensional electronic spectroscopy (2DES) is a powerful new technique for examining the electronic and vibronic couplings and dynamics of chemical, semiconductor, and biological samples. We present several technical innovations in the implementation of 2DES. We have performed two-color 2DES experiments, extending the technique's ability to study energy transfer to states at frequencies far from the initial absorption. We have demonstrated 2DES in the pump-probe geometry using a pulse-shaper. This method eliminates many technical challenges inherent to previous implementations of 2DES, making it a more widely accessible technique. To broaden the available frequency information, we have demonstrated 2DES with a continuum probe pulse. We have utilized this method to observe vibrational wavepacket dynamics in a laser dye, demonstrating that these dynamics modulate 2D lineshapes and must be accounted for in modelling 2DES data. We perform 2DES studies on the Qy band of the D1D2-cyt.b559 reaction center of plant photosystem II. This reaction center is the core oxygen-evolving complex in plant photosynthesis, taking in light energy and forming a charge separated state capable of splitting water. Understanding the relationship between the structure and function has both fundamental importance and applications to improving artificial light-harvesting. Traditional spectroscopy methods have been unable to completely resolve the time-ordering of energy and charge transfer events or the degree of electronic coupling between chromophores due to severe spectral congestion in the Q y band. 2DES extends previous methods by frequency-resolving an additional dimension to reveal the degree of static disorder and electronic coupling, as well as a detailed picture of energy and charge transfer dynamics that will allow tests of excitonic models of the reaction center. Our data show direct evidence of electronic coupling and rapid sub-ps energy transfer between "blue" and "red

  20. Energy Adventure Center. Activity Book. Revised [and Expanded] Edition.

    ERIC Educational Resources Information Center

    Wichita Unified School District 259, KS.

    A variety of energy activities are provided, including instructions for and questions related to energy films. The activities are organized into five sections. Section 1 (work) includes an activity focusing on movement and change. Section 2 (forms of energy) includes activities related to mechanical (movement), radiant (light), chemical (burning),…

  1. Photosynthetic antenna-reaction center mimicry with a covalently linked monostyryl boron-dipyrromethene-aza-boron-dipyrromethene-C60 triad.

    PubMed

    Shi, Wen-Jing; El-Khouly, Mohamed E; Ohkubo, Kei; Fukuzumi, Shunichi; Ng, Dennis K P

    2013-08-19

    An efficient functional mimic of the photosynthetic antenna-reaction center has been designed and synthesized. The model contains a near-infrared-absorbing aza-boron-dipyrromethene (ADP) that is connected to a monostyryl boron-dipyrromethene (BDP) by a click reaction and to a fullerene (C60 ) using the Prato reaction. The intramolecular photoinduced energy and electron-transfer processes of this triad as well as the corresponding dyads BDP-ADP and ADP-C60 have been studied with steady-state and time-resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge-separated states. Such calculations show that electron transfer from the singlet excited ADP ((1) ADP*) to C60 yielding ADP(.+) -C60 (.-) is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from (1) BDP* to ADP in the dyad BDP-ADP and electron transfer from (1) ADP* to C60 in the dyad ADP-C60 . Sequential energy and electron transfer have also been clearly observed in the triad BDP-ADP-C60 . By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈10(11)  s(-1) ). The dynamics of electron transfer through (1) ADP* has also been studied by monitoring the formation of C60 radical anion at 1000 nm. A fast charge-separation process from (1) ADP* to C60 has been detected, which gives the relatively long-lived BDP-ADP(.+) C60 (.-) with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge-separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state

  2. 34 CFR 350.32 - What activities must a Rehabilitation Engineering Research Center conduct?

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 34 Education 2 2010-07-01 2010-07-01 false What activities must a Rehabilitation Engineering... DISABILITY AND REHABILITATION RESEARCH PROJECTS AND CENTERS PROGRAM What Rehabilitation Engineering Research Centers Does the Secretary Assist? § 350.32 What activities must a Rehabilitation Engineering...

  3. 34 CFR 350.32 - What activities must a Rehabilitation Engineering Research Center conduct?

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 34 Education 2 2012-07-01 2012-07-01 false What activities must a Rehabilitation Engineering... DISABILITY AND REHABILITATION RESEARCH PROJECTS AND CENTERS PROGRAM What Rehabilitation Engineering Research Centers Does the Secretary Assist? § 350.32 What activities must a Rehabilitation Engineering...

  4. 34 CFR 350.32 - What activities must a Rehabilitation Engineering Research Center conduct?

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 34 Education 2 2011-07-01 2010-07-01 true What activities must a Rehabilitation Engineering... DISABILITY AND REHABILITATION RESEARCH PROJECTS AND CENTERS PROGRAM What Rehabilitation Engineering Research Centers Does the Secretary Assist? § 350.32 What activities must a Rehabilitation Engineering...

  5. 34 CFR 350.22 - What activities must a Rehabilitation Research and Training Center conduct?

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 34 Education 2 2010-07-01 2010-07-01 false What activities must a Rehabilitation Research and... DISABILITY AND REHABILITATION RESEARCH PROJECTS AND CENTERS PROGRAM What Rehabilitation Research and Training Centers Does the Secretary Assist? § 350.22 What activities must a Rehabilitation Research and...

  6. Physical Activity in Child-Care Centers: Do Teachers Hold the Key to the Playground?

    ERIC Educational Resources Information Center

    Copeland, Kristen A.; Kendeigh, Cassandra A.; Saelens, Brian E.; Kalkwarf, Heidi J.; Sherman, Susan N.

    2012-01-01

    Many (56%) US children aged 3-5 years are in center-based childcare and are not obtaining recommended levels of physical activity. In order to determine what child-care teachers/providers perceived as benefits and barriers to children's physical activity in child-care centers, we conducted nine focus groups and 13 one-on-one interviews with 49…

  7. Modeling of the D1/D2 proteins and cofactors of the photosystem II reaction center: implications for herbicide and bicarbonate binding.

    PubMed Central

    Xiong, J.; Subramaniam, S.; Govindjee

    1996-01-01

    A three-dimensional model of the photosystem II (PSII) reaction center from the cyanobacterium Synechocystis sp. PCC 6803 was generated based on homology with the anoxygenic purple bacterial photosynthetic reaction centers of Rhodobacter sphaeroides and Rhodopseudomonas viridis, for which the X-ray crystallographic structures are available. The model was constructed with an alignment of D1 and D2 sequences with the L and M subunits of the bacterial reaction center, respectively, and by using as a scaffold the structurally conserved regions (SCRs) from bacterial templates. The structurally variant regions were built using a novel sequence-specific approach of searching for the best-matched protein segments in the Protein Data Bank with the "basic local alignment search tool" (Altschul SF, Gish W, Miller W, Myers EW, Lipman DJ, 1990, J Mol Biol 215:403-410), and imposing the matching conformational preference on the corresponding D1 and D2 regions. The structure thus obtained was refined by energy minimization. The modeled D1 and D2 proteins contain five transmembrane alpha-helices each, with cofactors (4 chlorophylls, 2 pheophytins, 2 plastoquinones, and a non-heme iron) essential for PSII primary photochemistry embedded in them. A beta-carotene, considered important for PSII photoprotection, was also included in the model. Four different possible conformations of the primary electron donor P680 chlorophylls were proposed, one based on the homology with the bacterial template and the other three on existing experimental suggestions in literature. The P680 conformation based on homology was preferred because it has the lowest energy. Redox active tyrosine residues important for P680+ reduction as well as residues important for PSII cofactor binding were analyzed. Residues involved in interprotein interactions in the model were also identified. Herbicide 3-(3,4-dichlorophenyl)-1,1-dimethylurea (DCMU) was also modeled in the plastoquinone QB binding niche using the

  8. STS-26 Mission Control Center (MCC) activity at JSC

    NASA Technical Reports Server (NTRS)

    1988-01-01

    Flight controllers in JSC's Mission Control Center (MCC) Bldg 30 flight control room (FCR) listen to a presentation by STS-26 crewmembers on the fourth day of Discovery's, Orbiter Vehicle (OV) 103's, orbital mission. Flight Directors Charles W. Shaw and James M. (Milt) Heflin (in the foreground) and other controllers view a television image of Earth on a screen in the front of the FCR while listening to crewmembers.

  9. Aerospace Battery Activities at NASA/Goddard Space Flight Center

    NASA Technical Reports Server (NTRS)

    Rao, Gopalakrishna M.

    2006-01-01

    Goddard Space Flight Center has "pioneered" rechargeable secondary battery design, test, infusion and in-orbit battery management among NASA installations. Nickel cadmium batteries of various designs and sizes have been infused for LEO, GEO and Libration Point spacecraft. Nickel-Hydrogen batteries have currently been baselined for the majority of our missions. Li-Ion batteries from ABSL, JSB, SaFT and Lithion have been designed and tested for aerospace application.

  10. STS-26 Mission Control Center (MCC) activity at JSC

    NASA Technical Reports Server (NTRS)

    1988-01-01

    Flight controllers in JSC's Mission Control Center (MCC) Bldg 30 flight control room (FCR) listen to a presentation by STS-26 crewmembers on the fourth day of Discovery's, Orbiter Vehicle (OV) 103's, orbital mission. Instrumentation and Communications Officers (INCOs) Harold Black (left foreground) and John F. Muratore and other controllers view a television (TV) transmission of the crew on a screen in front of the FCR as each member relates some inner feelings while paying tribute to the 51L Challenger crew.

  11. Activities in Aeroelasticity at NASA Langley Research Center

    NASA Technical Reports Server (NTRS)

    Perry, Boyd, III; Noll, Thomas E.

    1997-01-01

    This paper presents the results of recently-completed research and presents status reports of current research being performed within the Aeroelasticity Branch of the NASA Langley Research Center. Within the paper this research is classified as experimental, analytical, and theoretical aeroelastic research. The paper also describes the Langley Transonic Dynamics Tunnel, its features, capabilities, a new open-architecture data acquisition system, ongoing facility modifications, and the subsequent calibration of the facility.

  12. Low-temperature (77 K) phosphorescence of triplet chlorophyll in isolated reaction centers of photosystem II.

    PubMed

    Neverov, Konstantin V; Krasnovsky, Alexander A; Zabelin, Alexey A; Shuvalov, Vladimir A; Shkuropatov, Anatoly Ya

    2015-08-01

    Phosphorescence characterized by the main emission band at 952 ± 1 nm (1.30 eV), the lifetime of 1.5 ± 0.1 ms and the quantum yield nearly equal to that for monomeric chlorophyll a in aqueous detergent dispersions, has been detected in isolated reaction centers (RCs) of spinach photosystem II at 77 K. The excitation spectrum shows maxima corresponding to absorption bands of chlorophyll a, pheophytin a, and β-carotene. The phosphorescence intensity strongly depends upon the redox state of RCs. The data suggest that the phosphorescence signal originates from the chlorophyll triplet state populated via charge recombination in the radical pair [Formula: see text].

  13. Classroom Activities: Simple Strategies to Incorporate Student-Centered Activities within Undergraduate Science Lectures.

    PubMed

    Lom, Barbara

    2012-01-01

    The traditional science lecture, where an instructor delivers a carefully crafted monolog to a large audience of students who passively receive the information, has been a popular mode of instruction for centuries. Recent evidence on the science of teaching and learning indicates that learner-centered, active teaching strategies can be more effective learning tools than traditional lectures. Yet most colleges and universities retain lectures as their central instructional method. This article highlights several simple collaborative teaching techniques that can be readily deployed within traditional lecture frameworks to promote active learning. Specifically, this article briefly introduces the techniques of: reader's theatre, think-pair-share, roundtable, jigsaw, in-class quizzes, and minute papers. Each technique is broadly applicable well beyond neuroscience courses and easily modifiable to serve an instructor's specific pedagogical goals. The benefits of each technique are described along with specific examples of how each technique might be deployed within a traditional lecture to create more active learning experiences.

  14. Comments on the optical lineshape function: Application to transient hole-burned spectra of bacterial reaction centers

    SciTech Connect

    Reppert, Mike; Kell, Adam; Pruitt, Thomas; Jankowiak, Ryszard

    2015-03-07

    The vibrational spectral density is an important physical parameter needed to describe both linear and non-linear spectra of multi-chromophore systems such as photosynthetic complexes. Low-temperature techniques such as hole burning (HB) and fluorescence line narrowing are commonly used to extract the spectral density for a given electronic transition from experimental data. We report here that the lineshape function formula reported by Hayes et al. [J. Phys. Chem. 98, 7337 (1994)] in the mean-phonon approximation and frequently applied to analyzing HB data contains inconsistencies in notation, leading to essentially incorrect expressions in cases of moderate and strong electron-phonon (el-ph) coupling strengths. A corrected lineshape function L(ω) is given that retains the computational and intuitive advantages of the expression of Hayes et al. [J. Phys. Chem. 98, 7337 (1994)]. Although the corrected lineshape function could be used in modeling studies of various optical spectra, we suggest that it is better to calculate the lineshape function numerically, without introducing the mean-phonon approximation. New theoretical fits of the P870 and P960 absorption bands and frequency-dependent resonant HB spectra of Rb. sphaeroides and Rps. viridis reaction centers are provided as examples to demonstrate the importance of correct lineshape expressions. Comparison with the previously determined el-ph coupling parameters [Johnson et al., J. Phys. Chem. 94, 5849 (1990); Lyle et al., ibid. 97, 6924 (1993); Reddy et al., ibid. 97, 6934 (1993)] is also provided. The new fits lead to modified el-ph coupling strengths and different frequencies of the special pair marker mode, ω{sub sp}, for Rb. sphaeroides that could be used in the future for more advanced calculations of absorption and HB spectra obtained for various bacterial reaction centers.

  15. Hydrogen bonds between nitrogen donors and the semiquinone in the Q(B) site of bacterial reaction centers.

    PubMed

    Martin, Erik; Samoilova, Rimma I; Narasimhulu, Kupala V; Wraight, Colin A; Dikanov, Sergei A

    2010-08-25

    Photosynthetic reaction centers from Rhodobacter sphaeroides have identical ubiquinone-10 molecules functioning as primary (Q(A)) and secondary (Q(B)) electron acceptors. X-band 2D pulsed EPR spectroscopy, called HYSCORE, was applied to study the interaction of the Q(B) site semiquinone with nitrogens from the local protein environment in natural and (15)N uniformly labeled reactions centers. (14)N and (15)N HYSCORE spectra of the Q(B) semiquinone show the interaction with two nitrogens carrying transferred unpaired spin density. Quadrupole coupling constants estimated from (14)N HYSCORE spectra indicate them to be a protonated nitrogen of an imidazole residue and amide nitrogen of a peptide group. (15)N HYSCORE spectra allowed estimation of the isotropic and anisotropic couplings with these nitrogens. From these data, we calculated the unpaired spin density transferred onto 2s and 2p orbitals of nitrogen and analyzed the contribution of different factors to the anisotropic hyperfine tensors. The hyperfine coupling of other protein nitrogens with the semiquinone is weak (<0.1 MHz). These results clearly indicate that the Q(B) semiquinone forms hydrogen bonds with two nitrogens and provide quantitative characteristics of the hyperfine couplings with these nitrogens, which can be used in theoretical modeling of the Q(B) site. On the basis of the quadrupole coupling constant, one nitrogen can only be assigned to N(delta) of His-L190, consistent with all existing structures. However, we cannot specify between two candidates the residue corresponding to the second nitrogen. Further work employing multifrequency spectroscopic approaches or selective isotope labeling would be desirable for unambiguous assignment of this nitrogen.

  16. Pressure-induced spectral changes for the special-pair radical cation of the bacterial photosynthetic reaction center.

    PubMed

    Leiger, Kristjan; Freiberg, Arvi; Dahlbom, Mats G; Hush, Noel S; Reimers, Jeffrey R

    2007-06-07

    The effect of pressure up to 6 kbars on the near to mid infrared absorption spectrum (7500-14,300 cm(-1) or 1333-700 nm) of the oxidized reaction center of Rhodobacter sphaeroides is measured and interpreted using density-functional B3LYP, INDO, and PM5 calculations. Two weak electronic transition origins at approximately 8010 and approximately 10,210 cm(-1) are unambiguously identified. The first transition is assigned to a Qy tripdoublet band that involves, in the localized description of the excitation, a triplet absorption on one of the bacteriochlorophyll molecules (PM) in the reaction center's special pair intensified by the presence of a radical cation on the other (PL). While most chlorophyll transition energies decrease significantly with increasing pressure, the tripdoublet band is found to be almost pressure insensitive. This difference is attributed to the additional increase in the tripdoublet-band energy accompanying compression of the pi-stacked special pair. The second band could either be the anticipated second Qy tripdoublet state, a Qx tripdoublet state, or a state involving excitation from a low-lying doubly occupied orbital to the half-occupied cationic orbital. A variety of absorption bands that are also resolved in the 8300-9600 cm(-1) region are assigned as vibrational structure associated with the first tripdoublet absorption. These sidebands are composites that are shown by the calculations to comprise many unresolved individual modes; while the calculated pressure sensitivity of each individual mode is small, the calculated pressure dependence of the combined sideband structure is qualitatively similar to the observed pressure dependence, preventing the positive identification of possible additional electronic transitions in this spectral region.

  17. Comments on the optical lineshape function: Application to transient hole-burned spectra of bacterial reaction centers

    NASA Astrophysics Data System (ADS)

    Reppert, Mike; Kell, Adam; Pruitt, Thomas; Jankowiak, Ryszard

    2015-03-01

    The vibrational spectral density is an important physical parameter needed to describe both linear and non-linear spectra of multi-chromophore systems such as photosynthetic complexes. Low-temperature techniques such as hole burning (HB) and fluorescence line narrowing are commonly used to extract the spectral density for a given electronic transition from experimental data. We report here that the lineshape function formula reported by Hayes et al. [J. Phys. Chem. 98, 7337 (1994)] in the mean-phonon approximation and frequently applied to analyzing HB data contains inconsistencies in notation, leading to essentially incorrect expressions in cases of moderate and strong electron-phonon (el-ph) coupling strengths. A corrected lineshape function L(ω) is given that retains the computational and intuitive advantages of the expression of Hayes et al. [J. Phys. Chem. 98, 7337 (1994)]. Although the corrected lineshape function could be used in modeling studies of various optical spectra, we suggest that it is better to calculate the lineshape function numerically, without introducing the mean-phonon approximation. New theoretical fits of the P870 and P960 absorption bands and frequency-dependent resonant HB spectra of Rb. sphaeroides and Rps. viridis reaction centers are provided as examples to demonstrate the importance of correct lineshape expressions. Comparison with the previously determined el-ph coupling parameters [Johnson et al., J. Phys. Chem. 94, 5849 (1990); Lyle et al., ibid. 97, 6924 (1993); Reddy et al., ibid. 97, 6934 (1993)] is also provided. The new fits lead to modified el-ph coupling strengths and different frequencies of the special pair marker mode, ωsp, for Rb. sphaeroides that could be used in the future for more advanced calculations of absorption and HB spectra obtained for various bacterial reaction centers.

  18. Mechanistic Insights into the Carbon Dioxide/Cyclohexene Oxide Copolymerization Reaction: Is One Metal Center Enough?

    PubMed

    González-Fabra, Joan; Castro-Gómez, Fernando; Kleij, Arjan W; Bo, Carles

    2017-03-22

    A detailed study on the mechanism for the alternating copolymerization of cyclohexene oxide (CHO) and CO2 mediated by an [Al{amino-tri(phenolate)}]/NBu4 I binary catalyst system was performed by using DFT-based methods. Four potential mechanisms (one monometallic and three bimetallic) were considered for the first propagation cycle of the CHO/CO2 copolymerization. The obtained Gibbs free energies provided a rationale for the relative high activity of a non-covalent dimeric structure formed in situ and thus for the feasibility of a bimetallic mechanism to obtain polycarbonates quantitatively. Gibbs free energies also indicated that the alternating copolymerization was favored over the cyclic carbonate formation.

  19. Photoreduction and reoxidation of the three iron-sulfur clusters of reaction centers of green sulfur bacteria.

    PubMed

    Sétif, P; Seo, D; Sakurai, H

    2001-09-01

    Iron-sulfur clusters are the terminal electron acceptors of the photosynthetic reaction centers of green sulfur bacteria and photosystem I. We have studied electron-transfer reactions involving these clusters in the green sulfur bacterium Chlorobium tepidum, using flash-absorption spectroscopic measurements. We show for the first time that three different clusters, named F(X), F(1), and F(2), can be photoreduced at room temperature during a series of consecutive flashes. The rates of electron escape to exogenous acceptors depend strongly upon the number of reduced clusters. When two or three clusters are reduced, the escape is biphasic, with the fastest phase being 12-14-fold faster than the slowest phase, which is similar to that observed after single reduction. This is explained by assuming that escape involves mostly the second reducible cluster. Evidence is thus provided for a functional asymmetry between the two terminal acceptors F(1) and F(2). From multiple-flash experiments, it was possible to derive the intrinsic recombination rates between P840(+) and reduced iron-sulfur clusters: values of 7, 14, and 59 s(-1) were found after one, two and three electron reduction of the clusters, respectively. The implications of our results for the relative redox potentials of the three clusters are discussed.

  20. Mutation-induced perturbation of the special pair P840 in the homodimeric reaction center in green sulfur bacteria.

    PubMed

    Azai, Chihiro; Sano, Yuko; Kato, Yuki; Noguchi, Takumi; Oh-oka, Hirozo

    2016-01-25

    Homodimeric photosynthetic reaction centers (RCs) in green sulfur bacteria and heliobacteria are functional homologs of Photosystem (PS) I in oxygenic phototrophs. They show unique features in their electron transfer reactions; however, detailed structural information has not been available so far. We mutated PscA-Leu688 and PscA-Val689 to cysteine residues in the green sulfur bacterium Chlorobaculum tepidum; these residues were predicted to interact with the special pair P840, based on sequence comparison with PS I. Spectroelectrochemical measurements showed that the L688C and V689C mutations altered a near-infrared difference spectrum upon P840 oxidation, as well as the redox potential of P840. Light-induced Fourier transform infrared difference measurements showed that the L688C mutation induced a differential signal of the S-H stretching vibration in the P840(+)/P840 spectrum, as reported in P800(+)/P800 difference spectrum in a heliobacterial RC. Spectral changes in the 13(1)-keto C=O region, caused by both mutations, revealed corresponding changes in the electronic structure of P840 and in the hydrogen-bonding interaction at the 13(1)-keto C=O group. These results suggest that there is a common spatial configuration around the special pair sites among type 1 RCs. The data also provided evidence that P840 has a symmetric electronic structure, as expected from a homodimeric RC.

  1. Synchronizing Substrate Activation Rates in Multicomponent Reactions with Metal-Organic Framework Catalysts.

    PubMed

    Aguirre-Díaz, Lina María; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles

    2016-05-04

    A study on the influence of the cation coordination number, number of Lewis acid centers, concurrent existence of Lewis base sites, and structure topology on the catalytic activity of six new indium MOFs, has been carried out for multicomponent reactions (MCRs). The new indium polymeric frameworks, namely [In8 (OH)6 (popha)6 (H2 O)4 ]⋅3 H2 O (InPF-16), [In(popha)(2,2'-bipy)]⋅3 H2 O (InPF-17), [In3 (OH)3 (popha)2 (4,4'-bipy)]⋅4 H2 O (InPF-18), [In2 (popha)2 (4,4'-bipy)2 ]⋅3 H2 O (InPF-19), [In(OH)(Hpopha)]⋅0.5 (1,7-phen) (InPF-20), and [In(popha)(1,10-phen)]⋅4 H2 O (InPF-21) (InPF=indium polymeric framework, H3 popha=5-(4-carboxy-2-nitrophenoxy)isophthalic acid, phen=phenanthroline, bipy=bipyridine), have been hydrothermally obtained by using both conventional heating (CH) and microwave (MW) procedures. These indium frameworks show efficient Lewis acid behavior for the solvent-free cyanosilylation of carbonyl compounds, the one pot Passerini 3-component (P-3CR) and the Ugi 4-component (U-4CR) reactions. In addition, InPF-17 was found to be a highly reactive, recyclable, and environmentally benign catalyst, which allows the efficient synthesis of α-aminoacyl amides. The relationship between the Lewis base/acid active site and the catalytic performance is explained by the 2D seven-coordinated indium framework of the catalyst InPF-17. This study is an attempt to highlight the main structural and synthetic factors that have to be taken into account when planning a new, effective MOF-based heterogeneous catalyst for multicomponent reactions.

  2. Self-assembled biomimetic nanoreactors II: Noble metal active centers

    NASA Astrophysics Data System (ADS)

    McTaggart, Matt; Malardier-Jugroot, Cecile; Jugroot, Manish

    2015-09-01

    The structure and stability of polymer-metal nanoreactors is detailed, including a complete characterization of the first successful synthesis of stable, dispersible, atomically thin gold nanosheets. Further developments in the synthesis of monodisperse, ∼2.5 nm platinum nanoclusters in aqueous solution and ambient conditions are described and pH stability of the composite material is established. The facile nanoreactor synthesis, environmentally friendly reaction conditions, and structural stability makes these biomimetic systems attractive for applications ranging from chemical detoxification to nanoelectronics.

  3. Recent Activities on the Embrace Space Weather Regional Warning Center: the New Space Weather Data Center

    NASA Astrophysics Data System (ADS)

    Denardini, Clezio Marcos; Dal Lago, Alisson; Mendes, Odim; Batista, Inez S.; SantAnna, Nilson; Gatto, Rubens; Takahashi, Hisao; Costa, D. Joaquim; Banik Padua, Marcelo; Campos Velho, Haroldo

    2016-07-01

    On August 2007 the National Institute for Space Research started a task force to develop and operate a space weather program, which is known by the acronyms Embrace that stands for the Portuguese statement "Estudo e Monitoramento BRAasileiro de Clima Espacial" Program (Brazilian Space Weather Study and Monitoring program). The mission of the Embrace/INPE program is to monitor the Solar-Terrestrial environment, the magnetosphere, the upper atmosphere and the ground induced currents to prevent effects on technological and economic activities. The Embrace/INPE system monitors the physical parameters of the Sun-Earth environment, such as Active Regions (AR) in the Sun and solar radiation by using radio telescope, Coronal Mass Ejection (CME) information by satellite and ground-based cosmic ray monitoring, geomagnetic activity by the magnetometer network, and ionospheric disturbance by ionospheric sounders and using data collected by four GPS receiver network, geomagnetic activity by a magnetometer network, and provides a forecasting for Total Electronic Content (TEC) - 24 hours ahead - using a version of the SUPIM model which assimilates the two latter data using nudging approach. Most of these physical parameters are daily published on the Brazilian space weather program web portal, related to the entire network sensors available. Regarding outreach, it has being published a daily bulletin in Portuguese and English with the status of the space weather environment on the Sun, the Interplanetary Medium and close to the Earth. Since December 2011, all these activities are carried out at the Embrace Headquarter, a building located at the INPE's main campus. Recently, a comprehensive data bank and an interface layer are under commissioning to allow an easy and direct access to all the space weather data collected by Embrace through the Embrace web Portal. The information being released encompasses data from: (a) the Embrace Digisonde Network (Embrace DigiNet) that monitors

  4. Activities of the Structures Division, Lewis Research Center

    NASA Technical Reports Server (NTRS)

    1990-01-01

    The purpose of the NASA Lewis Research Center, Structures Division's 1990 Annual Report is to give a brief, but comprehensive, review of the technical accomplishments of the Division during the past calendar year. The report is organized topically to match the Center's Strategic Plan. Over the years, the Structures Division has developed the technology base necessary for improving the future of aeronautical and space propulsion systems. In the future, propulsion systems will need to be lighter, to operate at higher temperatures and to be more reliable in order to achieve higher performance. Achieving these goals is complex and challenging. Our approach has been to work cooperatively with both industry and universities to develop the technology necessary for state-of-the-art advancement in aeronautical and space propulsion systems. The Structures Division consists of four branches: Structural Mechanics, Fatigue and Fracture, Structural Dynamics, and Structural Integrity. This publication describes the work of the four branches by three topic areas of Research: (1) Basic Discipline; (2) Aeropropulsion; and (3) Space Propulsion. Each topic area is further divided into the following: (1) Materials; (2) Structural Mechanics; (3) Life Prediction; (4) Instruments, Controls, and Testing Techniques; and (5) Mechanisms. The publication covers 78 separate topics with a bibliography containing 159 citations. We hope you will find the publication interesting as well as useful.

  5. Recent and future Stratospheric Balloon Activities at Esrange Space Center

    NASA Astrophysics Data System (ADS)

    Kemi, Stig

    2012-07-01

    PlaceNameEsrange PlaceNameSpace PlaceTypeCenter located in northern country-regionplaceSweden has during 45 years been a leading launch site for both sounding rockets and stratospheric balloons. We have an unique combination of maintaining both stratospheric balloons and sounding rockets launch operations. Most balloon flights are normally handled inside Scandinavia but since 2005 PersonNamesemi-circular flights are performed with recovery in northern country-regionplaceCanada. The Swedish and Russian Governments have signed an agreement for peaceful exploration of space on 19 March 2010, which will permit circumpolar balloon flights. Within this agreement we are able to offer the science community long duration balloon flights in the Northern Hemisphere with durations for PersonNameseveral weeks. The balloon operations at placePlaceNameEsrange PlaceNameSpace PlaceTypeCenter are yearly expanding. Both NASA and CNES have long term plans for balloon flights from northern country-regionplaceSweden. We have also received requests from placePlaceNameJapanese PlaceTypeUniversities and JAXA for future balloon missions. To handle balloon campaigns with large numbers of payloads or build up for two different campaigns a new big assembly hall was ready for use in April 2011. Circumpolar balloon flights from PlaceNameplaceEsrange PlaceNameSpace PlaceTypeCenter are possible due to the specific conditions during the Arctic summer with continuous daylight and nearly constant solar heating keeping the balloon at a constant altitude with a minimum of ballast. In total 10 payloads have been flying for 4 to 5 days from Esrange westwards with landing in northern Canada since 2005. The SUNRISE balloon borne solar telescope is one example which made in June metricconverterProductID2009 a2009 a more than 4 days semi-circular balloon flight from Esrange. The CitySunrise project is a collaborative project between the Max Planck Institute for Solar System Research in Katlenburg-Lindau and

  6. EPR and optical spectroscopic properties of the electron carrier intermediate between the reaction center bacteriochlorophylls and the primary acceptor in Chromatium vinosum.

    PubMed

    Tiede, D M; Prince, R C; Dutton, P L

    1976-12-06

    1. A reaction center-cytochrome c complex has been isolated from Chromatium vinosum which is capable of normal photochemistry and light-activated rapid cytochrome c553 and c555 oxidation, but which has no antenna bacteriochlorophyll. As is found in whole cells, ferrocytochrome c553 is oxidized irreversibly in milliseconds by light at 7 K. 2. Room temperature redox potentiometry in combination with EPR analysis at 7 K, of cytochrome c553 and the reaction center bacteriochlorophyll dimer (BChl)2 absorbing at 883 nm yields identical results to those previously reported using optical analytical techniques at 77 K. It shows directly that two cytochrome c553 hemes are equivalent with respect to the light induced (BChl)2+. At 7 K, only one heme can be rapidly oxidized in the light, commensurate with the electron capacity of the primary acceptor (quinone-iron) being unity. 3. Prior chemical reduction of the quinone-iron followed by illumination at 200K, however, leads to the slow (t1/2 approximately equal to 30 s) oxidation of one cytochrome c553 heme, with what appears to be concommitant reduction of one of the two bacteriophytins (BPh) of the reaction center as shown by bleaching of the 760 nm band, a broad absorbance increase at approx. 650 nm and a bleaching at 543 nm. The 800 nm absorbing bacteriochlorophyll is also involved since there is also bleaching at 595 and 800 nm; at the latter wave-length the remaining unbleached band appears to shift significantly to the blue. No redox changes in the 883 absorbing bacteriochlorophyll dimer are seen during or after illumination under these conditions. The reduced part of the state represents what is considered to be the reduced form of the electron carrier (I) which acts as an intermediate between the bacteriochlorophyll dimer and quinone-iron. The state (oxidized c553/reduced I) relaxes in the dark at 200K in t1/2 approx. 20 min but below 77 K it is trapped on a days time scale. 4. EPR analysis of the state trapped as

  7. Report on Advanced Life Support Activities at Kennedy Space Center

    NASA Technical Reports Server (NTRS)

    Wheeler, Raymond M.

    2004-01-01

    Plant studies at Kennedy Space Center last year focused on selecting cultivars of lettuce, tomato, and pepper for further testing as crops for near-term space flight applications. Other testing continued with lettuce, onion, and radish plants grown at different combinations of light (PPF), temperature, and CO2 concentration. In addition, comparisons of mixed versus mono culture approaches for vegetable production were studied. Water processing testing focused on the development and testing of a rotating membrane bioreactor to increase oxygen diffusion levels for reducing total organic carbon levels and promoting nitrification. Other testing continued to study composting testing for food wastes (NRA grant) and the use of supplemental green light with red/blue LED lighting systems for plant production (NRC fellowship).

  8. [Activities of Goddard Earth Sciences and Technology Center, Maryland University

    NASA Technical Reports Server (NTRS)

    2003-01-01

    The Goddard Space Flight Center (GSFC) is recognized as a world leader in the application of remote sensing and modeling aimed at improving knowledge of the Earth system. The Goddard Earth Sciences Directorate plays a central role in NASA's Earth Observing System and the U.S. Global Change Research Program. Goddard Earth Sciences and Technology (GEST) is organized as a cooperative agreement with the GSFC to promote excellence in the Earth sciences, and is a consortium of universities and corporations (University of Maryland Baltimore County, Howard University, Hampton University, Caelum Research Corporation and Northrop Grumman Corporation). The aim of this new program is to attract and introduce promising students in their first or second year of graduate studies to Oceanography and Earth system science career options through hands-on instrumentation research experiences on coastal processes at NASA's Wallops Flight Facility on the Eastern Shore of Virginia.

  9. NASA. Marshall Space Flight Center Hydrostatic Bearing Activities

    NASA Technical Reports Server (NTRS)

    Benjamin, Theodore G.

    1991-01-01

    The basic approach for analyzing hydrostatic bearing flows at the Marshall Space Flight Center (MSFC) is briefly discussed. The Hydrostatic Bearing Team has responsibility for assessing and evaluating flow codes; evaluating friction, ignition, and galling effects; evaluating wear; and performing tests. The Office of Aerospace and Exploration Technology Turbomachinery Seals Tasks consist of tests and analysis. The MSFC in-house analyses utilize one-dimensional bulk-flow codes. Computational fluid dynamics (CFD) analysis is used to enhance understanding of bearing flow physics or to perform parametric analysis that are outside the bulk flow database. As long as the bulk flow codes are accurate enough for most needs, they will be utilized accordingly and will be supported by CFD analysis on an as-needed basis.

  10. Recent and Future Stratospheric Balloon Activities at Esrange Space Center

    NASA Astrophysics Data System (ADS)

    Kemi, Stig

    Esrange Space Center located in northern Sweden has during 45 years been a leading launch site for both sounding rockets and stratospheric balloons. We have a unique combination of maintaining both stratospheric balloons and sounding rockets launch operations. Most balloon flights are normally handled inside Scandinavia but since 2005 PersonNamesemi-circular flights are performed with recovery in northern Canada. The Swedish Government and Swedish National Space Board are now finaliz-ing an agreement with Russia for peaceful uPersonNamese of space, which will permit circumpolar balloon flights. Within this agreement we will soon be able to of-fer the science community long duration balloon flights with durations for PersonNameseveral weeks. The balloon operations at Esrange Space Center are yearly expanding. Both NASA and CNES have long term plans for balloon flights from northern Sweden. We have also received a request from JAXA for future balloon missions. To handle balloon campaigns with large numbers of payloads or build up for two different campaigns a new big assembly hall will be ready for use at the beginning of 2011. January 24 we made an historical balloon flight in a very cold stratosphere with a Zodiac metricconverterProductID402?000 m3402ü ınbsp;000 m3402 000 m3 balloon carrying a 750kg gondola with the German Mipas-B/Telis instrument. The balloon reached 34kms alti-tude after a carefully piloted ascent in temperature levels down to -89 degrees Centigrade. The scientists received unique data during the 13 hours and 30 minutes long sailing at different altitudes during slow descent. The payload was recovered in very good condition 80 kms from the border between country-regionFinland and Russia.

  11. Activation energy for a model ferrous-ferric half reaction from transition path sampling.

    PubMed

    Drechsel-Grau, Christof; Sprik, Michiel

    2012-01-21

    Activation parameters for the model oxidation half reaction of the classical aqueous ferrous ion are compared for different molecular simulation techniques. In particular, activation free energies are obtained from umbrella integration and Marcus theory based thermodynamic integration, which rely on the diabatic gap as the reaction coordinate. The latter method also assumes linear response, and both methods obtain the activation entropy and the activation energy from the temperature dependence of the activation free energy. In contrast, transition path sampling does not require knowledge of the reaction coordinate and directly yields the activation energy [C. Dellago and P. G. Bolhuis, Mol. Simul. 30, 795 (2004)]. Benchmark activation energies from transition path sampling agree within statistical uncertainty with activation energies obtained from standard techniques requiring knowledge of the reaction coordinate. In addition, it is found that the activation energy for this model system is significantly smaller than the activation free energy for the Marcus model, approximately half the value, implying an equally large entropy contribution.

  12. Reaction of germinal centers in the T-cell-independent response to the bacterial polysaccharide alpha(1-->6)dextran.

    PubMed Central

    Wang, D; Wells, S M; Stall, A M; Kabat, E A

    1994-01-01

    Primary immunization of BALB/c mice with alpha(1-->6)dextran (DEX), a native bacterial polysaccharide, induces an unexpected pattern of splenic B-cell responses. After a peak of antibody-secreting B-cell response at day 4, deposition of dextran-anti-dextran immune complexes, as revealed by staining with both dextran and antibodies to dextran, occurs and persists in splenic follicles until at least the fourth week after immunization. Antigen-specific B cells appear and proliferate in such follicles, leading by day 11 to development of DEX-specific germinal centers as characterized by the presence of distinct regions of DEX+ peanut agglutinin-positive (PNA+) cells. At this time, fluorescence-activated cell sorter analysis also reveals the appearance of a distinct population of DEX+ PNA+ splenic B cells. In contrast, DEX+ PNA- cells, characterized by intense cytoplasmic staining, are present outside of splenic follicles, peak at day 4 to day 5, and persist until at least day 28. The frequency of these cells correlates with DEX-specific antibody-secreting cells, as detected by the ELISA-spot assay. Thus, in addition to the expected plasma cellular response, the typical T-cell-independent type II antigen, DEX, surprisingly also elicits the formation of antigen-specific germinal centers. These observations raise fundamental questions about the roles of germinal centers in T-cell-independent immune responses. Images PMID:7511812

  13. Formation of quaternary stereogenic centers by copper-catalyzed asymmetric conjugate addition reactions of alkenylaluminums to trisubstituted enones.

    PubMed

    Müller, Daniel; Alexakis, Alexandre

    2013-11-04

    Alkenylaluminums undergo asymmetric copper-catalyzed conjugate addition (ACA) to β-substituted enones allowing the formation of stereogenic all-carbon quaternary centers. Phosphinamine-copper complexes proved to be particularly active and selective compared with phosphoramidite ligands. After extensive optimization, high enantioselectivities (up to 96% ee) were obtained for the addition of alkenylalanes to β-substituted enones. Two strategies for the generation of the requisite alkenylaluminums were explored allowing for the introduction of aryl- and alkyl-substituted alkenyl nucleophiles. Moreover, alkyl-substituted phosphinamine (SimplePhos) ligands were identified for the first time as highly efficient ligands for the Cu-catalyzed ACA.

  14. Proton ENDOR study of the primary donor P740 +, a special pair of chlorophyll d in photosystem I reaction center of Acaryochloris marina

    NASA Astrophysics Data System (ADS)

    Mino, Hiroyuki; Kawamori, Asako; Aoyama, Daisuke; Tomo, Tatsuya; Iwaki, Masayo; Itoh, Shigeru

    2005-08-01

    Oxidized primary electron donor P740, a special pair of chlorophyll (Chl) d in photosystem (PS) I reaction center of a newly identified cyanobacterium Acaryochloris marina was studied by EPR and proton ENDOR spectroscopy. EPR and ENDOR spectra of P740 + were compared with those of P700 + in PS I reaction center of spinach. The g-factors of the purified Chl a+ and Chl d+ in CH 2Cl 2/THF, P700 + and P740 + in PS I reaction centers were determined to be 2.0025, 2.0032, 2.0027 and 2.0028, respectively. Hyperfine coupling constants of 1.9, 2.8 and 3.8 MHz that were detected in the ENDOR spectrum of P700 + were absent in the ENDOR spectrum of P740 +. These features of P740 + were mainly ascribed to the difference between the chemical structures of Chl a and Chl d.

  15. Activated by Combined Magnrtic Field Gravitropic Reaction Reply on Nanodose of Biologicaly Active Compounds

    NASA Astrophysics Data System (ADS)

    Sheykina, Nadezhda; Bogatina, Nina

    The new science direction nanotechnologies initiated a big jump in the pharmacology and medicine. This leads to the big development of homeopathy. The most interest appeared while investigating of the reaction of biological object on the nano dose of iologically substances. The changing of concentration (in nmol/l) of biologically active material is also possible during weak energy action. For instance, weak combined magnetic field may change a little the concentration of ions that are oriented parallel to the external magnetic field and, by the analogy with said above, lead to the similar effects. Simple estimations give the value for the threshold to the magnetic field by two orders smaller than the geomagnetic field. By this investigation we wanted to understand whether the analogy in the action of nano dose of biologically active substances and weak combined magnetic field presents and whether the action of one of these factors may be replaced by other one. The effect of one of biologically active substances NPA (Naphtyl-Phtalame Acid) solution with the concentration 0.01 mol/l on the gravitropic reaction of cress roots was investigated. It was shown that its effect was the inhibition of cress roots gravitropic reaction. The same inhibition was achieved by the combined magnetic field action on the cress roots, germinated in water. The alternative component of the combined magnetic field coincided formally with the cyclotron frequency of NPA ions. So the analogy in the action of nano dose of biologically active substances and weak combined magnetic field was shown. The combined magnetic field using allows to decrease sufficiently the dose of biologically active substances. This fact can be of great importance in pharmacy and medicine.

  16. 77 FR 70211 - Agency Information Collection Activities (Call Center Satisfaction Survey) Under OMB Review

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-11-23

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF VETERANS AFFAIRS Agency Information Collection Activities (Call Center Satisfaction Survey) Under OMB Review AGENCY....'' SUPPLEMENTARY INFORMATION: Title: VBA Call Center Satisfaction Survey. OMB Control Number: 2900-0744. Type...

  17. GREENHOUSE GAS (GHG) MITIGATION AND MONITORING TECHNOLOGY PERFORMANCE: ACTIVITIES OF THE GHG TECHNOLOGY VERIFICATION CENTER

    EPA Science Inventory

    The paper discusses greenhouse gas (GHG) mitigation and monitoring technology performance activities of the GHG Technology Verification Center. The Center is a public/private partnership between Southern Research Institute and the U.S. EPA's Office of Research and Development. It...

  18. A Guide to Establishing an Activity Center for Mentally Retarded Persons.

    ERIC Educational Resources Information Center

    Bergman, Allan

    The guide contains basic information for establishing a work activity center, a work-oriented facility providing compensatory pre-vocational and vocational education and training programs for men and women of post-school age. The center serves those mentally retarded adults not developmentally prepared to enter a sheltered workshop program. The…

  19. Social Inequalities in Body Weight and Physical Activity: Exploring the Role of Fitness Centers

    ERIC Educational Resources Information Center

    McLaren, Lindsay; Rock, Melanie J.; McElgunn, Jamie

    2012-01-01

    Fitness centers are a viable option for physical activity, particularly in climates with significant weather variation. Due to variation in economic and social expressions of exclusivity, fitness centers may have some relation to social inequalities in physical inactivity and related health outcomes; thus, our objective was to explore this…

  20. B-branch electron transfer in reaction centers of Rhodobacter sphaeroides assessed with site-directed mutagenesis.

    PubMed

    de Boer, Arjo L; Neerken, Sieglinde; de Wijn, Rik; Permentier, Hjalmar P; Gast, Peter; Vijgenboom, Erik; Hoff, Arnold J

    2002-01-01

    Mutants of Rhodobacter (Rba.) sphaeroides are described which were designed to study electron transfer along the so-called B-branch of reaction center (RC) cofactors. Combining the mutation L(M214)H, which results in the incorporation of a bacteriochlorophyll, beta, for H(A) [Kirmaier et al. (1991) Science 251: 922-927] with two mutations, G(M203)D and Y(M210)W, near B(A), we have created a double and a triple mutant with long lifetimes of the excited state P(*) of the primary donor P, viz. 80 and 160 ps at room temperature, respectively. The yield of P(+)Q(A) (-) formation in these mutants is reduced to 50 and 30%, respectively, of that in wildtype RCs. For both mutants, the quantum yield of P(+)H(B) (-) formation was less than 10%, in contrast to the 15% B-branch electron transfer demonstrated in RCs of a similar mutant of Rba. capsulatus with a P(*) lifetime of 15 ps [Heller et al. (1995) Science 269: 940-945]. We conclude that the lifetime of P(*) is not a governing factor in switching to B-branch electron transfer. The direct photoreduction of the secondary quinone, Q(B), was studied with a triple mutant combining the G(M203)D, L(M214)H and A(M260)W mutations. In this triple mutant Q(A) does not bind to the reaction center [Ridge et al. (1999) Photosynth Res 59: 9-26]. It is shown that B-branch electron transfer leading to P(+)Q(B) (-) formation occurs to a minor extent at both room temperature and at cryogenic temperatures (about 3% following a saturating laser flash at 20 K). In contrast, in wildtype RCs P(+)Q(B) (-) formation involves the A-branch and does not occur at all at cryogenic temperatures. Attempts to accumulate the P(+)Q(B) (-) state under continuous illumination were not successful. Charge recombination of P(+)Q(B) (-) formed by B-branch electron transfer in the new mutant is much faster (seconds) than has been previously reported for charge recombination of P(+)Q(B) (-) trapped in wildtype RCs (10(5) s) [Kleinfeld et al. (1984b) Biochemistry 23

  1. Excited-state electronic asymmetry of the special pair in photosynthetic reaction center mutants: absorption and Stark spectroscopy.

    PubMed

    Moore, L J; Zhou, H; Boxer, S G

    1999-09-14

    The electronic absorption line shape and Stark spectrum of the lowest energy Q(y)() transition of the special pair in bacterial reaction centers contain a wealth of information on mixing with charge transfer states and electronic asymmetry. Both vary greatly in mutants that perturb the chemical composition of the special pair, such as the heterodimer mutants, and in mutants that alter interactions between the special pair and the surrounding reaction center protein, such as those that add or remove hydrogen bonds. The conventional and higher-order Stark spectra of a series of mutants are presented with the aim of developing a systematic description of the electronic structure of the excited state of the special pair that initiates photosynthetic charge separation. The mutants L168HF, M197FH, L131LH and L131LH/M160LH/M197FH are known to have different hydrogen-bonding patterns to the special pair; however, they exhibit Stark effects that are very similar to wild type. By contrast, the addition of a hydrogen bond to the M-side keto carbonyl group of the special pair in M160LH greatly affects both the absorption and Stark spectra. The heterodimer special pairs, L173HL and M202HL, exhibit much larger Stark effects than wild type, with the greatest effect in the M-side mutant. Double mutants that combine the M-side heterodimer and a hydrogen-bond addition to the L-side of the special pair decrease the magnitude of the Stark effect. These results suggest that the electronic asymmetry of the dimer can be perturbed either by the formation of a heterodimer or by adding or deleting a hydrogen bond to a keto carbonyl group. From the pattern observed, it is concluded that the charge transfer state P(L)(+)P(M)(-) has a larger influence on the excited state of the dimer in wild type than the P(L)(-)P(M)(+)charge transfer state. Furthermore, asymmetry can be varied continuously, from extreme cases in which the heterodimer and hydrogen-bond effects work together, to cases in which

  2. Hydrogen bonding and spin density distribution in the Qb semiquinone of bacterial reaction centers and comparison with the Qa site.

    PubMed

    Martin, Erik; Samoilova, Rimma I; Narasimhulu, Kupala V; Lin, Tzu-Jen; O'Malley, Patrick J; Wraight, Colin A; Dikanov, Sergei A

    2011-04-13

    In the photosynthetic reaction center from Rhodobacter sphaeroides, the primary (Q(A)) and secondary (Q(B)) electron acceptors are both ubiquinone-10, but with very different properties and functions. To investigate the protein environment that imparts these functional differences, we have applied X-band HYSCORE, a 2D pulsed EPR technique, to characterize the exchangeable protons around the semiquinone (SQ) in the Q(A) and Q(B) sites, using samples of (15)N-labeled reaction centers, with the native high spin Fe(2+) exchanged for diamagnetic Zn(2+), prepared in (1)H(2)O and (2)H(2)O solvent. The powder HYSCORE method is first validated against the orientation-selected Q-band ENDOR study of the Q(A) SQ by Flores et al. (Biophys. J.2007, 92, 671-682), with good agreement for two exchangeable protons with anisotropic hyperfine tensor components, T, both in the range 4.6-5.4 MHz. HYSCORE was then applied to the Q(B) SQ where we found proton lines corresponding to T ≈ 5.2, 3.7 MHz and T ≈ 1.9 MHz. Density functional-based quantum mechanics/molecular mechanics (QM/MM) calculations, employing a model of the Q(B) site, were used to assign the observed couplings to specific hydrogen bonding interactions with the Q(B) SQ. These calculations allow us to assign the T = 5.2 MHz proton to the His-L190 N(δ)H···O(4) (carbonyl) hydrogen bonding interaction. The T = 3.7 MHz spectral feature most likely results from hydrogen bonding interactions of O1 (carbonyl) with both Gly-L225 peptide NH and Ser-L223 hydroxyl OH, which possess calculated couplings very close to this value. The smaller 1.9 MHz coupling is assigned to a weakly bound peptide NH proton of Ile-L224. The calculations performed with this structural model of the Q(B) site show less asymmetric distribution of unpaired spin density over the SQ than seen for the Q(A) site, consistent with available experimental data for (13)C and (17)O carbonyl hyperfine couplings. The implications of these interactions for Q

  3. Transmission research activities at NASA Lewis Research Center

    NASA Technical Reports Server (NTRS)

    Lewicki, D. G.

    1990-01-01

    A joint research program, to advance the technology of rotorcraft transmissions, consists of analytical and experimental efforts to achieve the overall goals of reducing transmission weight and noise, while increasing life and reliability. Recent activities in the areas of transmission and related component research are highlighted. Current areas include specific technologies in support of military rotary wing aviation, gearing technology, transmission noise reduction studies, a recent interest in gearbox diagnostics, and advanced transmission system studies. Results of recent activities are presented along with near term research plans.

  4. A new perspective on the radio active zone at the Galactic center - feedback from nuclear activities

    NASA Astrophysics Data System (ADS)

    Zhao, J.-H.; Morris, M. R.; Goss, W. M.

    2014-05-01

    Based on our deep image of Sgr A using broadband data observed with the VLA† at 6 cm, we present a new perspective of the radio bright zone at the Galactic center. We further show the radio detection of the X-ray Cannonball, a candidate neutron star associated with the Galactic center SNR Sgr A East. The radio image is compared with the Chandra X-ray image to show the detailed structure of the radio counterparts of the bipolar X-ray lobes. The bipolar lobes are likely produced by the winds from the activities within Sgr A West, which could be collimated by the inertia of gas in the CND, or by the momentum driving of Sgr A*; and the poloidal magnetic fields likely play an important role in the collimation. The less-collimated SE lobe, in comparison to the NW one, is perhaps due to the fact that the Sgr A East SN might have locally reconfigured the magnetic field toward negative galactic latitudes. In agreement with the X-ray observations, the time-scale of ˜1 × 104 yr estimated for the outermost radio ring appears to be comparable to the inferred age of the Sgr A East SNR.

  5. Asymmetric Catalytic aza-Morita-Baylis-Hillman Reaction for the Synthesis of 3-Substituted-3-Aminooxindoles with Chiral Quaternary Carbon Centers

    PubMed Central

    Hu, Fang-Le; Wei, Yin; Shi, Min; Pindi, Suresh; Li, Guigen

    2013-01-01

    Asymmetric catalytic aza-Morita-Baylis-Hillman (aza-MBH) reaction of isatin-derived ketimines with MVK has been established by using chiral amino and phosphino catalysts. The reaction resulted in biomedically important 3-substituted 3-amino-2-oxindoles in good yields (>80% for most cases) and excellent enantioselectivity (90–99%ee). Twenty-eight cases assembled with chiral quaternary stereogenic centers have been examined under convenient systems. PMID:23407608

  6. Robotics-Centered Outreach Activities: An Integrated Approach

    ERIC Educational Resources Information Center

    Ruiz-del-Solar, Javier

    2010-01-01

    Nowadays, universities are making extensive efforts to attract prospective students to the fields of electrical, electronic, and computer engineering. Thus, outreach is becoming increasingly important, and activities with schoolchildren are being extensively carried out as part of this effort. In this context, robotics is a very attractive and…

  7. Kidspiration[R] for Inquiry-Centered Activities

    ERIC Educational Resources Information Center

    Shaw, Edward L., Jr.; Baggett, Paige V.; Salyer, Barbara

    2004-01-01

    Computer technology can be integrated into science inquiry activities to increase student motivation and enhance and expand scientific thinking. Fifth-grade students used the visual thinking tools in the Kidspiration[R] software program to generate and represent a web of hypotheses around the question, "What affects the distance a marble rolls?"…

  8. UAS Related Activities at NASA's Dryden Flight Research Center

    NASA Technical Reports Server (NTRS)

    Bauer, Jeffrey E.

    2009-01-01

    NASA s Dryden Flight Research Center is completing its refurbishment and initial flights of one the pre-production Global Hawk aircraft it received from the U.S. Air Force. NASA Dryden has an agreement with the Global Hawk s manufacturer, Northrop Grumman, to partner in the refurbishment and flight operations of the vehicles. The National Oceanic and Atmospheric Administration (NOAA) has also partnered on the project and is assisting NASA with project management and pilot responsibilities for the aircraft. NASA and NOAA will be using the Global Hawks to conduct earth science research. The earth science community is increasing utilizing UAS of all sizes and capabilities to collect important data on a variety of issues including important global climate change issues. To pursue the data collection needs of the science community there is a growing demand for international collaboration with respect to operating UAS in global airspace. Operations of NASA s Ikhana aircraft continued this past year. The Ikhana is a modified Predator B UAS. A UAS dedicated to research at NASA Dryden is the X-48B blended wing body research aircraft. Flight tests with the 500- pound, remotely piloted test vehicle are now in a block 4 phase involving parameter identification and maneuvers to research the limits of the engine in stall situations. NASA s participation in the blended wing body research effort is focused on fundamental, advanced flight dynamics and structural design concepts within the Subsonic Fixed Wing project, part of the Fundamental Aeronautics program managed through NASA s Aeronautics Research Mission Directorate. Potential benefits of the aircraft include increased volume for carrying capacity, efficient aerodynamics for reduced fuel burn and possibly significant reductions in noise due to propulsion integration options. NASA Dryden continues to support the UAS industry by facilitating access to three specially designated test areas on Edwards Air Force Base for the

  9. Suboptimal B-cell antigen receptor signaling activity in vivo elicits germinal center counterselection mechanisms.

    PubMed

    Königsberger, Sebastian; Weis, Vanessa; Prodöhl, Jan; Stehling, Martin; Hobeika, Elias; Reth, Michael; Kiefer, Friedemann

    2015-02-01

    Syk and Zap-70 constitute a closely related nonreceptor protein tyrosine kinase family, of which both members are functionally indispensable for conferring their respective antigen receptors with enzymatic activity. In this study, we analyze the impact of altering BCR signaling output on B-cell germinal center (GC) fate selection by constitutive, as well as inducible, monoallelic Syk kinase loss in the presence of a Zap-70 knock-in rescue allele. Cre-mediated Syk deletion in Syk(flox/Zap-70) B cells lowers pErk, but not pAkt-mediated signaling. Surprisingly, the use of a B-cell-specific constitutive mb1-cre deleter mouse model showed that a small cohort of peripheral Syk(flox/Zap-70);mb1-cre B cells efficiently circumvents deletion, which ultimately favors these Syk-sufficient cells to contribute to the GC reaction. Using a developmentally unbiased Syk(flox/Zap-70);mb1-creER(T2) approach in combination with an inducible tdRFP allele, we further demonstrate that this monoallelic deletion escape is not fully explained by leakiness of Cre expression, but is possibly the result of differential Syk locus accessibility in maturing B cells. Altogether, this underscores the importance of proper Syk kinase function not only during central and peripheral selection processes, but also during GC formation and maintenance.

  10. An Interactive Classroom Activity Demonstrating Reaction Mechanisms and Rate-Determining Steps

    ERIC Educational Resources Information Center

    Jennings, Laura D.; Keller, Steven W.

    2005-01-01

    An interactive classroom activity that includes two-step reaction of unwrapping and eating chocolate candies is described which brings not only the reaction intermediate, but also the reactants and products into macroscopic view. The qualitative activation barriers of both steps can be adjusted independently.

  11. Selenium-ligated palladium(II) complexes as highly active catalysts for carbon-carbon coupling reactions: the Heck reaction.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Zheng, Chong

    2004-08-19

    Three selenium-ligated Pd(II) complexes were readily synthesized and shown to be extremely active catalysts for the Heck reaction of various aryl bromides, including deactivated and heterocyclic ones. The catalytic activity of the selenide-based Pd(II) complexes not only rivals but vastly outperforms that of the corresponding phosphorus and sulfur analogues. Practical advantages of the selenium-based catalysts include their straightforward synthesis and high activity in the absence of any additives as well as the enhanced stability of the selenide ligands toward air oxidation.

  12. Classroom Activities: Simple Strategies to Incorporate Student-Centered Activities within Undergraduate Science Lectures

    PubMed Central

    Lom, Barbara

    2012-01-01

    The traditional science lecture, where an instructor delivers a carefully crafted monolog to a large audience of students who passively receive the information, has been a popular mode of instruction for centuries. Recent evidence on the science of teaching and learning indicates that learner-centered, active teaching strategies can be more effective learning tools than traditional lectures. Yet most colleges and universities retain lectures as their central instructional method. This article highlights several simple collaborative teaching techniques that can be readily deployed within traditional lecture frameworks to promote active learning. Specifically, this article briefly introduces the techniques of: reader’s theatre, think-pair-share, roundtable, jigsaw, in-class quizzes, and minute papers. Each technique is broadly applicable well beyond neuroscience courses and easily modifiable to serve an instructor’s specific pedagogical goals. The benefits of each technique are described along with specific examples of how each technique might be deployed within a traditional lecture to create more active learning experiences. PMID:23494568

  13. City Kids and City Critters! Activities for Urban Explorers from the Houston Arboretum & Nature Center.

    ERIC Educational Resources Information Center

    Roberts, Janet Wier; Huelbig, Carole

    This guide contains activities from the Houston Arboretum and Nature Center programs for children ages 8 to 12 years. The multisensory activities help students improve their observational skills and utilize activity sheets, journals, and hands-on projects to involve them. Children observe, draw, and photograph animals in their natural settings and…

  14. Large photocurrent response and external quantum efficiency in biophotoelectrochemical cells incorporating reaction center plus light harvesting complexes.

    PubMed

    Yaghoubi, Houman; Lafalce, Evan; Jun, Daniel; Jiang, Xiaomei; Beatty, J Thomas; Takshi, Arash

    2015-04-13

    Bacterial photosynthetic reaction centers (RCs) are promising materials for solar energy harvesting, due to their high ratio of photogenerated electrons to absorbed photons and long recombination time of generated charges. In this work, photoactive electrodes were prepared from a bacterial RC-light-harvesting 1 (LH1) core complex, where the RC is encircled by the LH1 antenna, to increase light capture. A simple immobilization method was used to prepare RC-LH1 photoactive layer. Herein, we demonstrate that the combination of pretreatment of the RC-LH1 protein complexes with quinone and the immobilization method results in biophotoelectrochemical cells with a large peak transient photocurrent density and photocurrent response of 7.1 and 3.5 μA cm(-2), respectively. The current study with monochromatic excitation showed maximum external quantum efficiency (EQE) and photocurrent density of 0.21% and 2 μA cm(-2), respectively, with illumination power of ∼6 mW cm(-2) at ∼875 nm, under ambient conditions. This work provides new directions to higher performance biophotoelectrochemical cells as well as possibly other applications of this broadly functional photoactive material.

  15. Reaction Control System Thruster Cracking Consultation: NASA Engineering and Safety Center (NESC) Materials Super Problem Resolution Team (SPRT) Findings

    NASA Technical Reports Server (NTRS)

    MacKay, Rebecca A.; Smith, Stephen W.; Shah, Sandeep R.; Piascik, Robert S.

    2005-01-01

    The shuttle orbiter s reaction control system (RCS) primary thruster serial number 120 was found to contain cracks in the counter bores and relief radius after a chamber repair and rejuvenation was performed in April 2004. Relief radius cracking had been observed in the 1970s and 1980s in seven thrusters prior to flight; however, counter bore cracking had never been seen previously in RCS thrusters. Members of the Materials Super Problem Resolution Team (SPRT) of the NASA Engineering and Safety Center (NESC) conducted a detailed review of the relevant literature and of the documentation from the previous RCS thruster failure analyses. It was concluded that the previous failure analyses lacked sufficient documentation to support the conclusions that stress corrosion cracking or hot-salt cracking was the root cause of the thruster cracking and lacked reliable inspection controls to prevent cracked thrusters from entering the fleet. The NESC team identified and performed new materials characterization and mechanical tests. It was determined that the thruster intergranular cracking was due to hydrogen embrittlement and that the cracking was produced during manufacturing as a result of processing the thrusters with fluoride-containing acids. Testing and characterization demonstrated that appreciable environmental crack propagation does not occur after manufacturing.

  16. Redox potential tuning through differential quinone binding in the photosynthetic reaction center of Rhodobacter sphaeroides

    SciTech Connect

    Vermaas, Josh V.; Taguchi, Alexander T.; Dikanov, Sergei A.; Wraight, Colin A.; Tajkhorshid, Emad

    2015-03-03

    Ubiquinone forms an integral part of the electron transport chain in cellular respiration and photosynthesis across a vast number of organisms. Prior experimental results have shown that the photosynthetic reaction center (RC) from Rhodobacter sphaeroides is only fully functional with a limited set of methoxy-bearing quinones, suggesting that specific interactions with this substituent are required to drive electron transport and the formation of quinol. The nature of these interactions has yet to be determined. Through parameterization of a CHARMM-compatible quinone force field and subsequent molecular dynamics simulations of the quinone-bound RC, in this paper we have investigated and characterized the interactions of the protein with the quinones in the QA and QB sites using both equilibrium simulation and thermodynamic integration. In particular, we identify a specific interaction between the 2-methoxy group of ubiquinone in the QB site and the amide nitrogen of GlyL225 that we implicate in locking the orientation of the 2-methoxy group, thereby tuning the redox potential difference between the quinones occupying the QA and QB sites. Finally, disruption of this interaction leads to weaker binding in a ubiquinone analogue that lacks a 2-methoxy group, a finding supported by reverse electron transfer electron paramagnetic resonance experiments of the QA–QB– biradical and competitive binding assays.

  17. Equilibration kinetics in isolated and membrane-bound photosynthetic reaction centers upon illumination: a method to determine the photoexcitation rate.

    PubMed

    Manzo, Anthony J; Goushcha, Alexander O; Barabash, Yuri M; Kharkyanen, Valery N; Scott, Gary W

    2009-07-01

    Kinetics of electron transfer, following variation of actinic light intensity, for photosynthetic reaction centers (RCs) of purple bacteria (isolated and membrane-bound) were analyzed by measuring absorbance changes in the primary photoelectron donor absorption band at 865 nm. The bleaching of the primary photoelectron donor absorption band in RCs, following a sudden increase of illumination from the dark to an actinic light intensity of I(exp), obeys a simple exponential law with the rate constant alphaI(exp) + k(rec), in which alpha is a parameter relating the light intensity, measured in mW/cm(2), to a corresponding theoretical rate in units of reciprocal seconds, and k(rec) is the effective rate constant of the charge recombination in the photosynthetic RCs. In this work, a method for determining the alpha parameter value is developed and experimentally verified for isolated and membrane-bound RCs, allowing for rigorous modeling of RC macromolecule dynamics under varied photoexcitation conditions. Such modeling is necessary for RCs due to alterations of the forward photoexcitation rates and relaxation rates caused by illumination history and intramolecular structural dynamics effects. It is demonstrated that the classical Bouguer-Lambert-Beer formalism can be applied for the samples with relatively low scattering, which is not necessarily the case with strongly scattering media or high light intensity excitation.

  18. Electrostatic calculations of amino acid titration and electron transfer, Q-AQB-->QAQ-B, in the reaction center.

    PubMed Central

    Beroza, P; Fredkin, D R; Okamura, M Y; Feher, G

    1995-01-01

    The titration of amino acids and the energetics of electron transfer from the primary electron acceptor (QA) to the secondary electron acceptor (QB) in the photosynthetic reaction center of Rhodobacter sphaeroides are calculated using a continuum electrostatic model. Strong electrostatic interactions between titrating sites give rise to complex titration curves. Glu L212 is calculated to have an anomalously broad titration curve, which explains the seemingly contradictory experimental results concerning its pKa. The electrostatic field following electron transfer shifts the average protonation of amino acids near the quinones. The pH dependence of the free energy between Q-AQB and QAQ-B calculated from these shifts is in good agreement with experiment. However, the calculated absolute free energy difference is in severe disagreement (by approximately 230 meV) with the observed experimental value, i.e., electron transfer from Q-A to QB is calculated to be unfavorable. The large stabilization energy of the Q-A state arises from the predominantly positively charged residues in the vicinity of QA in contrast to the predominantly negatively charged residues near QB. The discrepancy between calculated and experimental values for delta G(Q-AQB-->QAQ-B) points to limitations of the continuum electrostatic model. Inclusion of other contributions to the energetics (e.g., protein motion following quinone reduction) that may improve the agreement between theory and experiment are discussed. PMID:7647231

  19. Constraint based scheduling for the Goddard Space Flight Center distributed Active Archive Center's data archive and distribution system

    NASA Technical Reports Server (NTRS)

    Short, Nick, Jr.; Bedet, Jean-Jacques; Bodden, Lee; Boddy, Mark; White, Jim; Beane, John

    1994-01-01

    The Goddard Space Flight Center (GSFC) Distributed Active Archive Center (DAAC) has been operational since October 1, 1993. Its mission is to support the Earth Observing System (EOS) by providing rapid access to EOS data and analysis products, and to test Earth Observing System Data and Information System (EOSDIS) design concepts. One of the challenges is to ensure quick and easy retrieval of any data archived within the DAAC's Data Archive and Distributed System (DADS). Over the 15-year life of EOS project, an estimated several Petabytes (10(exp 15)) of data will be permanently stored. Accessing that amount of information is a formidable task that will require innovative approaches. As a precursor of the full EOS system, the GSFC DAAC with a few Terabits of storage, has implemented a prototype of a constraint-based task and resource scheduler to improve the performance of the DADS. This Honeywell Task and Resource Scheduler (HTRS), developed by Honeywell Technology Center in cooperation the Information Science and Technology Branch/935, the Code X Operations Technology Program, and the GSFC DAAC, makes better use of limited resources, prevents backlog of data, provides information about resources bottlenecks and performance characteristics. The prototype which is developed concurrently with the GSFC Version 0 (V0) DADS, models DADS activities such as ingestion and distribution with priority, precedence, resource requirements (disk and network bandwidth) and temporal constraints. HTRS supports schedule updates, insertions, and retrieval of task information via an Application Program Interface (API). The prototype has demonstrated with a few examples, the substantial advantages of using HTRS over scheduling algorithms such as a First In First Out (FIFO) queue. The kernel scheduling engine for HTRS, called Kronos, has been successfully applied to several other domains such as space shuttle mission scheduling, demand flow manufacturing, and avionics communications

  20. Effects of reaction time variability and age on brain activity during Stroop task performance.

    PubMed

    Tam, Angela; Luedke, Angela C; Walsh, Jeremy J; Fernandez-Ruiz, Juan; Garcia, Angeles

    2015-09-01

    Variability in reaction time during task performance may reflect fluctuations in attention and cause reduced performance in goal-directed tasks, yet it is unclear whether the mechanisms behind this phenomenon change with age. Using fMRI, we tested young and cognitively healthy older adults with the Stroop task to determine whether aging affects the neural mechanisms underlying intra-individual reaction time variability. We found significant between-group differences in BOLD activity modulated by reaction time. In older adults, longer reaction times were associated with greater activity in frontoparietal attentional areas, while in younger adults longer reaction times were associated with greater activity in default mode network areas. Our results suggest that the neural correlates of reaction time variability change with healthy aging, reinforcing the concept of functional plasticity to maintain high cognitive function throughout the lifespan.

  1. "Monkey see, monkey do": Peers' behaviors predict preschoolers' physical activity and dietary intake in childcare centers.

    PubMed

    Ward, Stéphanie; Bélanger, Mathieu; Donovan, Denise; Boudreau, Jonathan; Vatanparast, Hassan; Muhajarine, Nazeem; Leis, Anne; Humbert, M Louise; Carrier, Natalie

    2017-04-01

    Preschoolers observe and imitate the behaviors of those who are similar to them. Therefore, peers may be role models for preschoolers' dietary intake and physical activity in childcare centers. This study examined whether peers' behaviors predict change in preschoolers' dietary intake and physical activity in childcare centers over 9months. A total of 238 preschoolers (3 to 5years old) from 23 childcare centers in two Canadian provinces provided data at the beginning (October 2013 and 2014) and the end (June 2014 and 2015) of a 9-month period for this longitudinal study. Dietary intake was collected at lunch using weighed plate waste and digital photography on two consecutive weekdays. Physical activity was assessed using accelerometers over five days. Multilevel linear regressions were used to estimate the influence of peers' behaviors on preschoolers' change in dietary intake and physical activity over 9months. Results showed that preschoolers whose dietary intake or physical activity level deviated the most from those of their peers at the beginning of the year demonstrated greater change in their intakes and activity levels over 9months, which enabled them to become more similar to their peers (all β 95% CI ranged from -0.835 to -0.074). This study suggests that preschoolers' dietary intake and physical activity may be influenced by the behaviors of their peers in childcare centers. Since peers could play an important role in promoting healthy eating behaviors and physical activity in childcare centers, future studies should test interventions based on positive role modeling by children.

  2. Identification of general linear relationships between activation energies and enthalpy changes for dissociation reactions at surfaces.

    PubMed

    Michaelides, Angelos; Liu, Z-P; Zhang, C J; Alavi, Ali; King, David A; Hu, P

    2003-04-02

    The activation energy to reaction is a key quantity that controls catalytic activity. Having used ab inito calculations to determine an extensive and broad ranging set of activation energies and enthalpy changes for surface-catalyzed reactions, we show that linear relationships exist between dissociation activation energies and enthalpy changes. Known in the literature as empirical Brønsted-Evans-Polanyi (BEP) relationships, we identify and discuss the physical origin of their presence in heterogeneous catalysis. The key implication is that merely from knowledge of adsorption energies the barriers to catalytic elementary reaction steps can be estimated.

  3. Gold catalysts for pure hydrogen production in the water-gas shift reaction: activity, structure and reaction mechanism.

    PubMed

    Burch, Robbie

    2006-12-21

    The production of hydrogen containing very low levels of carbon monoxide for use in polymer electrolyte fuel cells requires the development of catalysts that show very high activity at low temperatures where the equilibrium for the removal of carbon monoxide using the water-gas shift reaction is favourable. It has been claimed that oxide-supported gold catalysts have the required high activity but there is considerable uncertainty in the literature about the feasibility of using these catalysts under real conditions. By comparing the activity of gold catalysts with that of platinum catalysts it is shown that well-prepared gold catalysts are significantly more active than the corresponding platinum catalysts. However, the method of preparation and pre-treatment of the gold catalysts is critical and activity variations of several orders of magnitude can be observed depending on the methods chosen. It is shown that an intimate contact between gold and the oxide support is important and any preparative procedure that does not generate such an interaction, or any subsequent treatment that can destroy such an interaction, may result in catalysts with low activity. The oxidation state and structure of active gold catalysts for the water-gas shift reaction is shown to comprise gold primarily in a zerovalent metallic state but in intimate contact with the support. This close contact between small metallic gold particles and the support may result in the "atoms" at the point of contact having a net charge (most probably cationic) but the high activity is associated with the presence of metallic gold. Both in situ XPS and XANES appear unequivocal on this point and this conclusion is consistent with similar measurements on gold catalysts even when used for CO oxidation. In situ EXAFS measurements under water gas shift conditions show that the active form of gold is a small gold cluster in intimate contact with the oxide support. The importance of the gold/oxide interface is

  4. The dual effects of Maillard reaction and enzymatic hydrolysis on the antioxidant activity of milk proteins.

    PubMed

    Oh, N S; Lee, H A; Lee, J Y; Joung, J Y; Lee, K B; Kim, Y; Lee, K W; Kim, S H

    2013-08-01

    The objective of this study was to determine the enhanced effects on the biological characteristics and antioxidant activity of milk proteins by the combination of the Maillard reaction and enzymatic hydrolysis. Maillard reaction products were obtained from milk protein preparations, such as whey protein concentrates and sodium caseinate with lactose, by heating at 55°C for 7 d in sodium phosphate buffer (pH 7.4). The Maillard reaction products, along with untreated milk proteins as controls, were hydrolyzed for 0 to 3h with commercial proteases Alcalase, Neutrase, Protamex, and Flavorzyme (Novozymes, Bagsværd, Denmark). The antioxidant activity of hydrolyzed Maillard reaction products was determined by reaction with 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt, their 1,1-diphenyl-2-picrylhydrazyl radical scavenging activity, and the ability to reduce ferric ions. Further characteristics were evaluated by the o-phthaldialdehyde method and sodium dodecyl sulfate-PAGE. The degree of hydrolysis gradually increased in a time-dependent manner, with the Alcalase-treated Maillard reaction products being the most highly hydrolyzed. Radical scavenging activities and reducing ability of hydrolyzed Maillard reaction products increased with increasing hydrolysis time. The combined products of enzymatic hydrolysis and Maillard reaction showed significantly greater antioxidant activity than did hydrolysates or Maillard reaction products alone. The hydrolyzed Maillard reaction products generated by Alcalase showed significantly higher antioxidant activity when compared with the other protease products and the antioxidant activity was higher for the whey protein concentrate groups than for the sodium caseinate groups. These findings indicate that Maillard reaction products, coupled with enzymatic hydrolysis, could act as potential antioxidants in the pharmaceutical, food, and dairy industries.

  5. Coevolution between human's anticancer activities and functional foods from crop origin center in the world.

    PubMed

    Zeng, Ya-Wen; Du, Juan; Pu, Xiao-Ying; Yang, Jia-Zhen; Yang, Tao; Yang, Shu-Ming; Yang, Xiao-Meng

    2015-01-01

    Cancer is the leading cause of death around the world. Anticancer activities from many functional food sources have been reported in years, but correlation between cancer prevalence and types of food with anticancer activities from crop origin center in the world as well as food source with human migration are unclear. Hunger from food shortage is the cause of early human evolution from Africa to Asia and later into Eurasia. The richest functional foods are found in crop origin centers, housing about 70% in the world populations. Crop origin centers have lower cancer incidence and mortality in the world, especially Central Asia, Middle East, Southwest China, India and Ethiopia. Asia and Africa with the richest anticancer crops is not only the most important evolution base of humans and origin center of anticancer functional crop, but also is the lowest mortality and incidence of cancers in the world. Cancer prevention of early human migrations was associated with functional foods from crop origin centers, especially Asia with four centers and one subcenter of crop origin, accounting for 58% of the world population. These results reveal that coevolution between human's anticancer activities associated with functional foods for crop origin centers, especially in Asia and Africa.

  6. An iridium-mediated C-H activation/CO2-carboxylation reaction of 1,1-bisdiphenylphosphinomethane.

    PubMed

    Langer, Jens; Fabra, María José; García-Orduña, Pilar; Lahoz, Fernando J; Görls, Helmar; Oro, Luis A; Westerhausen, Matthias

    2010-09-07

    The reaction of 1,1-bisdiphenylphosphinomethane (dppm, 4 eq.) with [IrCl(coe)(2)](2) results in a solvent dependent equilibrium from which the complexes [IrCl(dppm)(dppm-H)(H)] (1) and [Ir(dppm)(2)]Cl (2) were isolated. When 2 is dissolved in methanol, [IrCl(dppm)(2)(H)][OCH(3)] (4) is formed as dominant species in solution. The C-H activation reaction which leads to 1 and 4 can be suppressed by adding an additional dppm ligand per iridium center resulting in the formation of [Ir(dppm)(3)]Cl (5). If the reaction of dppm with [IrX(coe)(2)](2) (X = Cl, I) is performed under an atmosphere of CO(2) the complexes [IrX(dppm)(H){(Ph(2)P)(2)C-COOH}] (6: X = Cl; 7: X = I) are formed by a CH activation/CO(2) carboxylation sequence. The reaction of 6 with NH(4)PF yields [IrCl(dppm)(2)(H)]PF(6).(10). Additionally the lithium compounds [Li(dme)(2)(dppm-H)] (3) and [Li(dme){(Ph(2)P)(2)CHCOO}](2) (8) were prepared for comparison. The molecular structures of the compounds 1, 3, 5, 7, 8 and of the related iridium complex [IrCl(dppm)(2)(H)]I (11) are reported.

  7. Theoretical Study on Highly Active Bifunctional Metalloporphyrin Catalysts for the Coupling Reaction of Epoxides with Carbon Dioxide.

    PubMed

    Hasegawa, Jun-Ya; Miyazaki, Ray; Maeda, Chihiro; Ema, Tadashi

    2016-10-01

    Highly active bifunctional metalloporphyrin catalysts were developed for the coupling reaction of epoxides with CO2 to produce cyclic carbonates. The bifunctional catalysts have both quaternary ammonium halide groups and a metal center. To elucidate the roles of these catalytic groups, DFT calculations were performed. Control reactions using tetrabutylammonium halide as a catalyst were also investigated for comparison. In the present article, the results of our computational studies are overviewed. The computational results are consistent with the experimental data and are useful for elucidating the structure-activity relationship. The key features responsible for the high catalytic activity of the bifunctional catalysts are as follows: 1) the cooperative action of the halide anion (nucleophile) and the metal center (Lewis acid); 2) the near-attack conformation, leading to the efficient opening of the epoxide ring in the rate-determining step; and 3) the conformational change of the quaternary ammonium cation to stabilize various anionic species generated during catalysis, in addition to the robustness (thermostability) of the catalysts.

  8. Excitation energy pathways in the photosynthetic units of reaction center LM- and H-subunit deletion mutants of Rhodospirillum rubrum.

    PubMed

    Amarie, Sergiu; Lupo, Domenico; Lenz, Martin O; Saegesser, Rudolf; Ghosh, Robin; Wachtveitl, Josef

    2010-03-01

    Light-induced reaction dynamics of isolated photosynthetic membranes obtained from wild-type (WT) and reaction center (RC)-subunit deletion strains SPUHK1 (an H-subunit deletion mutant) and SK Delta LM (an (L+M) deletion mutant) of the purple non-sulphur bacterium Rhodospirillum rubrum have been investigated by femtosecond transient absorption spectroscopy. Upon excitation of the spirilloxanthin (Spx) S(2) state at 546 nm, of the bacteriochlorophyll Soret band at 388 nm and probing spectral regions, which are characteristic for carotenoids, similar dynamics in the SPUHK1, SK Delta LM and WT strains could be observed. The excitation of Spx S(2) is followed by the simultaneous population of the lower singlet excited states S(1) and S* which decay with lifetimes of 1.4 and 5 ps, respectively for the mutants, and 1.4 and 4 ps, respectively, for the wild-type. The excitation of the BChl Soret band is followed by relaxation into BChl lower excited states which compete with excitation energy transfer BChl-to-Spx. The deexcitation pathway BChl(Soret) --> Spx(S(2)) --> Spx(S(1)) occurs with the same transition rate for all investigated samples (WT, SPUHK1 and SK Delta LM). The kinetic traces measured for the Spx S(1) --> S(N) transition display similar behaviour for all samples showing a positive signal which increases within the first 400 fs (i.e. the time needed for the excitation energy to reach the Spx S(1) excited state) and decays with a lifetime of about 1.5 ps. This suggests that the Spx excited state dynamics in the investigated complexes do not differ significantly. Moreover, a longer excited state lifetime of BChl for SPUHK1 in comparison to WT was observed, consistent with a photochemical quenching channel present in the presence of RC. For long delay times, photobleaching of the RC special pair and an electrochromic blue shift of the monomeric BChl a can be observed only for the WT but not for the mutants. The close similarity of the excited state decay

  9. High yield of B-branch electron transfer in a quadruple reaction center mutant of the photosynthetic bacterium Rhodobacter sphaeroides.

    PubMed

    de Boer, Arjo L; Neerken, Sieglinde; de Wijn, Rik; Permentier, Hjalmar P; Gast, Peter; Vijgenboom, Erik; Hoff, Arnold J

    2002-03-05

    A new reaction center (RC) quadruple mutant, called LDHW, of Rhodobacter sphaeroides is described. This mutant was constructed to obtain a high yield of B-branch electron transfer and to study P(+)Q(B)(-) formation via the B-branch. The A-branch of the mutant RC contains two monomer bacteriochlorophylls, B(A) and beta, as a result of the H mutation L(M214)H. The latter bacteriochlorophyll replaces bacteriopheophytin H(A) of wild-type RCs. As a result of the W mutation A(M260)W, the A-branch does not contain the ubiquinone Q(A); this facilitates the study of P(+)Q(B)(-) formation. Furthermore, the D mutation G(M203)D introduces an aspartic acid residue near B(A). Together these mutations impede electron transfer through the A-branch. The B-branch contains two bacteriopheophytins, Phi(B) and H(B), and a ubiquinone, Q(B.) Phi(B) replaces the monomer bacteriochlorophyll B(B) as a result of the L mutation H(M182)L. In the LDHW mutant we find 35-45% B-branch electron transfer, the highest yield reported so far. Transient absorption spectroscopy at 10 K, where the absorption bands due to the Q(X) transitions of Phi(B) and H(B) are well resolved, shows simultaneous bleachings of both absorption bands. Although photoreduction of the bacteriopheophytins occurs with a high yield, no significant (approximately 1%) P(+)Q(B)(-) formation was found.

  10. Carbon Dioxide Information Analysis Center and World Data Center-A for atmospheric trace gases: FY 1993 activities

    SciTech Connect

    Cushman, R.M.; Stoss, F.W. |

    1994-01-01

    During the course of a fiscal year, Oak Ridge National Laboratory`s Carbon Dioxide Information Analysis Center (CDIAC) distributes thousands of specialty publications-numeric data packages (NDPs), computer model packages (CMPs), technical reports, public communication publications, newsletters, article reprints, and reference books-in response to requests for information related to global environmental issues, primarily those pertaining to climate change. CDIAC`s staff also provide technical responses to specific inquiries related to carbon dioxide (CO{sub 2}), other trace gases, and climate. Hundreds of referrals to other researchers, policy analysts, information specialists, or organizations are also facilitated by CDIAC`s staff. This report provides an account of the activities accomplished by CDIAC (including World Data Center-A for Atmospheric Trace Gases) during the period October 1, 1992, to September 30, 1993. An organizational overview of CDIAC and its staff is supplemented by a detailed description of inquiries received and CDIAC`s response to those inquiries. An analysis and description of the preparation and distribution of NDPS, CMPS, technical reports, newsletters, fact sheets, specialty publications, and reprints are provided. Comments and descriptions of CDIAC`s information management systems, professional networking, and special bilateral agreements are also presented.

  11. Primary centers and secondary concentrations of tectonic activity through time in the western hemisphere of Mars

    USGS Publications Warehouse

    Anderson, R.C.; Dohm, J.M.; Golombek, M.P.; Haldemann, A.F.C.; Franklin, B.J.; Tanaka, K.L.; Lias, J.; Peer, B.

    2001-01-01

    Five main stages of radial and concentric structures formed around Tharsis from the Noachian through the Amazonian as determined by geologic mapping of 24,452 structures within the stratigraphic framework of Mars and by testing their radial and concentric orientations. Tectonic activity peaked in the Noachian (stage 1) around the largest center, Claritas, an elongate center extending more than 20?? in latitude and defined by about half of the total grabens which are concentrated in the Syria Planum, Thaumasia, and Tempe Terra regions. During the Late Noachian and Early Hesperian (stage 2), extensional structures formed along the length of present-day Valles Marineris and in Thaumasia (with a secondary concentration near Warrego Vallis) radial to a region just to the south of the central margin of Valles Marineris. Early Hesperian (stage 3) radial grabens in Pavonis, Syria, Ulysses, and Tempe Terra and somewhat concentric wrinkle ridges in Lunae and Solis Plana and in Thaumasia, Sirenum, Memnonia, and Amazonis are centered northwest of Syria with secondary centers at Thaumasia, Tempe Terra, Ulysses Fossae, and western Valles Marineris. Late Hesperian/Early Amazonian (stage 4) structures around Alba Patera, the northeast trending alignment of Tharsis Montes, and Olympus Mons appears centered on Alba Patera. Stage 5 structures (Middle-Late Amazonian) represent the last pulse of Tharsis-related activity and are found around the large shield volcanoes and are centered near Pavonis Mons. Tectonic activity around Tharsis began in the Noachian and generally decreased through geologic time to the Amazonian. Statistically significant radial distributions of structures formed during each stage, centered at different locations within the higher elevations of Tharsis. Secondary centers of radial structures during many of the stages appear related to previously identified local magmatic centers that formed at different times and locations throughout Tharsis. Copyright 2001 by

  12. Quality-Assurance Plan for Water-Quality Activities in the USGS Ohio Water Science Center

    USGS Publications Warehouse

    Francy, Donna S.; Shaffer, Kimberly H.

    2008-01-01

    In accordance with guidelines set forth by the Office of Water Quality in the Water Resources Discipline of the U.S. Geological Survey, a quality-assurance plan has been written for use by the Ohio Water Science Center in conducting water-quality activities. This quality-assurance plan documents the standards, policies, and procedures used by the Ohio Water Science Center for activities related to the collection, processing, storage, analysis, and publication of water-quality data. The policies and procedures documented in this quality-assurance plan for water-quality activities are meant to complement the Ohio Water Science Center quality-assurance plans for water-quality monitors, the microbiology laboratory, and surface-water and ground-water activities.

  13. Activities. A Collection of Things to Do at the Environmental Learning Center, Isabella, Minnesota.

    ERIC Educational Resources Information Center

    Environmental Learning Center, Isabella, Minn.

    A collection of activities used successfully at the Environmental Learning Center in Isabella, Minnesota, are contained in this guide. Areas of study are perception and communication, mapping, weather, snow, soil, aquatics, trees, and animals. Within these areas is a number of related activities, each to be adapted to the appropriate grade level.…

  14. SPECIAL ACTIVITIES SUPPLEMENTAL TO AND RELATED TO THE ART PROGRAM AT DEEP RIVER OUTDOOR EDUCATION CENTER.

    ERIC Educational Resources Information Center

    Gary City Public School System, IN.

    A CURRICULUM GUIDE DEALING WITH VARIOUS SUBJECT AREAS WAS PREPARED FOR POSSIBLE STUDY ACTIVITIES THAT WOULD USE THE LEARNING RESOURCES AVAILABLE AT THE DEEP RIVER OUTDOOR EDUCATION CENTER IN GARY, INDIANA. ACTIVITIES GUIDES ARE PRESENTED FOR (1) ART ACTITIVIES RELATED TO DESIGN, COLOR, LANDSCAPE REPRESENTATION, PAPER CONSTRUCTION, DRAWING, PRINT…

  15. Active-Learning versus Teacher-Centered Instruction for Learning Acids and Bases

    ERIC Educational Resources Information Center

    Sesen, Burcin Acar; Tarhan, Leman

    2011-01-01

    Background and purpose: Active-learning as a student-centered learning process has begun to take more interest in constructing scientific knowledge. For this reason, this study aimed to investigate the effectiveness of active-learning implementation on high-school students' understanding of "acids and bases". Sample: The sample of this…

  16. Learner-Centered Activities from the DVD-Format "Crouching Tiger, Hidden Dragon."

    ERIC Educational Resources Information Center

    Lin, Li-Yun

    This paper demonstrates how Taiwanese English-as-a-Second-Language (ESL) college teachers and students collaborate and negotiate to design various learner-centered activities based on the Chinese film, "Crouching Tiger, Hidden Dragon." These activities are intended to enhance students' listening and speaking abilities. The paper…

  17. Activity in Mission Control Center during Apollo 12 lunar landing mission

    NASA Technical Reports Server (NTRS)

    1969-01-01

    Overal view of activity in the Mission Operations Control Room in the Mission Control Center, bldg 30, during the Apollo 12 lunar landing mission. When this picture was made the first Apollo 12 extravehicular activity was being televised from the surface of the Moon.

  18. View of activity in Mission Control Center during Lunar Module liftoff

    NASA Technical Reports Server (NTRS)

    1971-01-01

    A partial view of activity in the Mission Operations Control Room in the Mission Control Center during the liftoff of the Apollo 15 Lunar Module 'Falcon' ascent stage from the lunar surface. An RCA color television camera mounted on the Lunar Roving Vehicle made it possible for people on Earth to watch the Lunar Module (LM) launch from the Moon. Seated in the right foreground is Astronaut Edgar D. Mitchell, a spacecraft communicator. Note liftoff on the television monitor in the center background.

  19. De novo-designed metallopeptides with type 2 copper centers: modulation of reduction potentials and nitrite reductase activities.

    PubMed

    Yu, Fangting; Penner-Hahn, James E; Pecoraro, Vincent L

    2013-12-04

    Enzymatic reactions involving redox processes are highly sensitive to the local electrostatic environment. Despite considerable effort, the complex interactions among different influential factors in native proteins impede progress toward complete understanding of the structure-function relationship. Of particular interest is the type 2 copper center Cu(His)3, which may act as an electron transfer center in peptidylglycine α-hydroxylating monooxygenase (PHM) or a catalytic center in copper nitrite reductase (CuNiR). A de novo design strategy is used to probe the effect of modifying charged amino acid residues around, but not directly bound to, a Cu(His)3 center embedded in three-stranded coiled coils (TRI-H)3 [TRI-H = Ac-G WKALEEK LKALEEK LKALEEK HKALEEK G-NH2]. Specifically, the peptide TRI-EH (=TRI-HK22E) alters an important lysine to glutamate just above the copper binding center. With a series of TRI-EH peptides mutated below the metal center, we use a variety of spectroscopies (EPR, UV-vis, XAS) to show a direct impact on the protonation equilibria, copper binding affinities, reduction potentials, and nitrite reductase activities of these copper-peptide complexes. The potentials at a specific pH vary by 100 mV, and the nitrite reductase activities range over a factor of 4 in rates. We also observe that the affinities, potentials, and catalytic activities are strongly influenced by the pH conditions (pH 5.8-7.4). In general, Cu(II) affinities for the peptides are diminished at low pH values. The interplay among these factors can lead to a 200 mV shift in reduction potential across these peptides, which is determined by the pH-dependent affinities of copper in both oxidation states. This study illustrates the strength of de novo protein design in elucidating the influence of ionizable residues on a particular redox system, an important step toward understanding the factors that govern the properties of this metalloenzyme with a goal of eventually improving the

  20. An Activation Energy Experiment for a Second-Order Reaction in a Single Laboratory Period.

    ERIC Educational Resources Information Center

    Barile, Raymond C.; Michiels, Leo P.

    1983-01-01

    Describes modification of a chemical reaction to a single 4 1/2-hour laboratory period. Reaction kinetics between 2, 4-initrochlorobenzene and piperidine to form 2, 4-dinitrophenyl-piperidine and piperidinium hydrochloride are followed conductometrically at three temperatures to obtain data to calculate activation parameters. (Author/JN)

  1. Ligand-free Heck reaction: Pd(OAc)2 as an active catalyst revisited.

    PubMed

    Yao, Qingwei; Kinney, Elizabeth P; Yang, Zhi

    2003-09-19

    Palladium acetate was shown to be an extremely active catalyst for the Heck reaction of aryl bromides. Both the base and the solvent were found to have a fundamental influence on the efficiency of the reaction, with K(3)PO(4) and N,N-dimethylacetamide being the optimal base and solvent, respectively.

  2. High energy halogen atom reactions activated by nuclear transformations. Progress report, February 15, 1979-February 14, 1980

    SciTech Connect

    Rack, E.P.

    1980-02-01

    The program consists of six interrelated areas: (1) Reactions of iodine with alkenes and alkynes activated by radiative neutron capture and isomeric transition in low pressure gaseous systems employing additives and rare gas moderators, high pressure, and liquid systems. Special attention was given to the reactivity of excited complex formation and structural effects of electrophilic iodine attack on various pi-bond systems. (2) The gas-to-condensed phase transition in halogen high energy chemistry. Current interest involves the study of caging effects of an ice lattice on recombination reactions involving neutron-irradiated frozen aqueous solutions of halogenated organic and biochemical solutes in order to learn more about kinetic energy effects, halogen size, solute molecule size, steric effects and hydrogen bonding within an ice lattice cage. (3) Systematics of halogen hot atom reactions. The reactions of /sup 80m/Br, /sup 80/Br, /sup 82m/Br + /sup 82/Br, /sup 82/Br, /sup 82/Br, /sup 128/I, /sup 130/I, and /sup 130m/I + /sup 130/I activated by radiative neutron capture or isomeric transition in hydrocarbons and halo-substituted alkanes in low pressure and high pressure gaseous systems employing additives and rare gas moderators are currently being studied. (4) Mathematical and computer simulation studies of caging events within an ice lattice are being investigated. (5) At Brookhaven National Laboratory, cyclotron-produced chlorine and fluorine hot atoms substitution reactions with molecules possessing a single chiral center are under investigation to determine the role of hot atom kinetic energy, halogen atom, enantioner structure, steric effects and phase on the extent of substitution by retention of configuration or by Walden inversion. (6) The applications of high energy techniques and concepts to neutron activation analysis for trace element determinations in biological systems was continued.

  3. Two-step mechanism of photodamage to photosystem II: step 1 occurs at the oxygen-evolving complex and step 2 occurs at the photochemical reaction center.

    PubMed

    Ohnishi, Norikazu; Allakhverdiev, Suleyman I; Takahashi, Shunichi; Higashi, Shoichi; Watanabe, Masakatsu; Nishiyama, Yoshitaka; Murata, Norio

    2005-06-14

    Under strong light, photosystem II (PSII) of oxygenic photosynthetic organisms is inactivated, and this phenomenon is called photoinhibition. In a widely accepted model, photoinhibition is induced by excess light energy, which is absorbed by chlorophyll but not utilized in photosynthesis. Using monochromatic light from the Okazaki Large Spectrograph and thylakoid membranes from Thermosynechococcus elongatus, we observed that UV and blue light inactivated the oxygen-evolving complex much faster than the photochemical reaction center of PSII. These observations suggested that the light-induced damage was associated with a UV- and blue light-absorbing center in the oxygen-evolving complex of PSII. The action spectrum of the primary event in photodamage to PSII revealed the strong effects of UV and blue light and differed considerably from the absorption spectra of chlorophyll and thylakoid membranes. By contrast to the photoinduced inactivation of the oxygen-evolving complex in untreated thylakoid membranes, red light efficiently induced inactivation of the PSII reaction center in Tris-treated thylakoid membranes, and the action spectrum resembled the absorption spectrum of chlorophyll. Our observations suggest that photodamage to PSII occurs in two steps. Step 1 is the light-induced inactivation of the oxygen-evolving complex. Step 2, occurring after step 1 is complete, is the inactivation of the PSII reaction center by light absorbed by chlorophyll. We confirmed our model by illumination of untreated thylakoid membranes with blue and UV light, which inactivated the oxygen-evolving complex, and then with red light, which inactivated the photochemical reaction center.

  4. Core/shell face-centered tetragonal FePd/Pd nanoparticles as an efficient non-Pt catalyst for the oxygen reduction reaction

    DOE PAGES

    Zhu, Huiyuan; Jiang, Guangming; Zhang, Xu; ...

    2015-10-04

    We report the synthesis of core/shell face-centered tetragonal (fct)-FePd/Pd nanoparticles (NPs) via reductive annealing of core/shell Pd/Fe3O4 NPs followed by temperature-controlled Fe etching in acetic acid. Among three different kinds of core/shell FePd/Pd NPs studied (FePd core at similar to 8 nm and Pd shell at 0.27, 0.65, or 0.81 nm), the fct-FePd/Pd-0.65 NPs are the most efficient catalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO4 with Pt-like activity and durability. This enhanced ORR catalysis arises from the desired Pd lattice compression in the 0.65 nm Pd shell induced by the fct-FePd core. Lastly, our study offersmore » a general approach to enhance Pd catalysis in acid for ORB.« less

  5. Core/shell face-centered tetragonal FePd/Pd nanoparticles as an efficient non-Pt catalyst for the oxygen reduction reaction

    SciTech Connect

    Zhu, Huiyuan; Jiang, Guangming; Zhang, Xu; Shen, Bo; Wu, Liheng; Zhang, Sen; Lu, Gang; Wu, Zhongbiao; Sun, Shouheng

    2015-10-04

    We report the synthesis of core/shell face-centered tetragonal (fct)-FePd/Pd nanoparticles (NPs) via reductive annealing of core/shell Pd/Fe3O4 NPs followed by temperature-controlled Fe etching in acetic acid. Among three different kinds of core/shell FePd/Pd NPs studied (FePd core at similar to 8 nm and Pd shell at 0.27, 0.65, or 0.81 nm), the fct-FePd/Pd-0.65 NPs are the most efficient catalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO4 with Pt-like activity and durability. This enhanced ORR catalysis arises from the desired Pd lattice compression in the 0.65 nm Pd shell induced by the fct-FePd core. Lastly, our study offers a general approach to enhance Pd catalysis in acid for ORB.

  6. Isolation and in vitro phosphorylation of sensory transduction components controlling anaerobic induction of light harvesting and reaction center gene expression in Rhodobacter capsulatus.

    PubMed

    Inoue, K; Kouadio, J L; Mosley, C S; Bauer, C E

    1995-01-17

    Anaerobic induction of light harvesting and reaction center gene expression involves two transacting factors termed RegA and RegB. Sequence and mutational analysis has indicated that RegA and RegB constitute cognate components of a prokaryotic sensory transduction cascade with RegB comprising a membrane-spanning sensor kinase and RegA a cytosolic response regulator. In this study we have purified RegA, as well as a truncated portion of RegB (RegB') and undertaken an in vitro analysis of autophosphorylation and phosphotransfer activities. Incubation of RegB' with [gamma-32P]ATP and MgCl2 resulted in phosphorylation of RegB' (RegB' approximately P) over a 20-min incubation period. Incubation of RegB' approximately P with RegA resulted in rapid transfer of the phosphate from RegB' to RegA. In analogy to other characterized prokaryotic sensory transduction components, mutational and chemical stability studies also indicate that RegB' is autophosphorylated at a conserved histidine and that RegA accepts the phosphate from RegB at a conserved aspartate.

  7. The Sugar Model: Autocatalytic Activity of the Triose-Ammonia Reaction

    NASA Technical Reports Server (NTRS)

    Weber, Arthur L.

    2006-01-01

    Reaction of triose sugars with ammonia under anaerobic conditions yielded autocatalytic products. The autocatalytic behavior of the products was examined by measuring the effect of the crude triose-ammonia reaction product on the kinetics of a second identical triose-ammonia reaction. The reaction product showed autocatalytic activity by increasing both the rate of disappearance of triose and the rate formation of pyruvaldehyde, the product of triose dehydration. This synthetic process is considered a reasonable model of origin-of-life chemistry because it uses plausible prebiotic substrates, and resembles modern biosynthesis by employing the energized carbon groups of sugars to drive the synthesis of autocatalytic molecules.

  8. The rate of second electron transfer to QB(-) in bacterial reaction center of impaired proton delivery shows hydrogen-isotope effect.

    PubMed

    Maróti, Ágnes; Wraight, Colin A; Maróti, Péter

    2015-02-01

    The 2nd electron transfer in reaction center of photosynthetic bacterium Rhodobacter sphaeroides is a two step process in which protonation of QB(-) precedes interquinone electron transfer. The thermal activation and pH dependence of the overall rate constants of different RC variants were measured and compared in solvents of water (H2O) and heavy water (D2O). The electron transfer variants where the electron transfer is rate limiting (wild type and M17DN, L210DN and H173EQ mutants) do not show solvent isotope effect and the significant decrease of the rate constant of the second electron transfer in these mutants is due to lowering the operational pKa of QB(-)/QBH: 4.5 (native), 3.9 (L210DN), 3.7 (M17DN) and 3.1 (H173EQ) at pH7. On the other hand, the proton transfer variants where the proton transfer is rate limiting demonstrate solvent isotope effect of pH-independent moderate magnitude (2.11±0.26 (WT+Ni(2+)), 2.16±0.35 (WT+Cd(2+)) and 2.34±0.44 (L210DN/M17DN)) or pH-dependent large magnitude (5.7 at pH4 (L213DN)). Upon deuteration, the free energy and the enthalpy of activation increase in all proton transfer variants by about 1 kcal/mol and the entropy of activation becomes negligible in L210DN/M17DN mutant. The results are interpreted as manifestation of equilibrium and kinetic solvent isotope effects and the structural, energetic and kinetic possibility of alternate proton delivery pathways are discussed.

  9. Electrochemical Dealloying of PdCu3 Nanoparticles to Achieve Pt-like Activity for the Hydrogen Evolution Reaction.

    PubMed

    Jana, Rajkumar; Bhim, Anupam; Bothra, Pallavi; Pati, Swapan K; Peter, Sebastian C

    2016-10-20

    Manipulating the d-band center of the metal surface and hence optimizing the free energy of hydrogen adsorption (ΔGH ) close to the optimal adsorption energy (ΔGH =0) for hydrogen evolution reaction (HER), is an efficient strategy to enhance the activity for HER. Herein, we report a oleylamine-mediated (acting as the solvent, stabilizer, and reducing agent) strategy to synthesize intermetallic PdCu3 nanoparticles (NPs) without using any external reducing agent. Upon electrochemical cycling, PdCu3 transforms into Pd-rich PdCu (ΔGH =0.05 eV), exhibiting remarkably enhanced activity (with a current density of 25 mA cm(-2) at ∼69 mV overpotential) as an alternative to Pt for HER. The first-principle calculation suggests that formation of low coordination number Pd active sites alters the d-band center and hence optimal adsorption of hydrogen, leading to enhanced activity. This finding may provide guidelines towards the design and development of Pt-free highly active and robust electrocatalysts.

  10. Generalization of the Activated Complex Theory of Reaction Rates. I. Quantum Mechanical Treatment

    DOE R&D Accomplishments Database

    Marcus, R. A.

    1964-01-01

    In its usual form activated complex theory assumes a quasi-equilibrium between reactants and activated complex, a separable reaction coordinate, a Cartesian reaction coordinate, and an absence of interaction of rotation with internal motion in the complex. In the present paper a rate expression is derived without introducing the Cartesian assumption. The expression bears a formal resemblance to the usual one and reduces to it when the added assumptions of the latter are introduced.

  11. Formation of P{sup +}Q{sub B}{sup -} via B-branch electron transfer in mutant reaction centers.

    SciTech Connect

    Laible, P. D.

    1998-08-14

    The crystallographic observation of two symmetry-related branches of electron transfer cofactors in the structure of the bacterial reaction center (RC) 13 years ago [1] remains an enigma in light of experimental observations that show that only the A branch is active in the initial electron transfer steps in wild-type RCs. Unidirectional electron flow has been attributed to localized asymmetries between the A and B branches that lead to differences in: (1) the electronic couplings of the cofactors [2]; (2) the relative electrostatic environments of the cofactors, caused by amino acid differences which modulate the free energies of their charge-separated states [3] and/or create a higher dielectric constant on the active side, resulting in a stronger static field for stabilizing A-branch charge transfer states [4,5]. Some photo-induced bleaching of H{sub B} has been observed, in wild-type RCs following trapping of HA{sub A}{sup {minus}}[6], and in ''hybrid'' RCs where the redox potentials of cofactors were manipulated by pigment exchange [7] or mutagenesis [8]. Transient bleaching of the 530-nm band of H{sub B} was more easily observed in the hybrid RCs because the H{sub A} transition at 545 nm was shifted to {approximately}600 nm due to incorporation of a bacteriochlorophyll, designated ''{beta}'', at the H{sub A} site. No experiments to detect further electron transfer to Q{sub B} were done with either type of modified RCs. Many site-specific mutagenesis experiments have given us insight into the nature and magnitude of the effects that amino acid side chains can exert in tuning the relative energy levels of the cofactors to optimize the balance between forward and reverse reactions, and the large distances through which some of these effects are manifested. In this paper, we show that in mutant RCs of Rhodobacter capsulatus, P{sup +}Q{sub B}{sup {minus}} can be formed in the absence of prior formation of P{sup +}Q{sub A}{sup {minus}}, solely through activity of B

  12. DISCOVERY OF THE RECOMBINING PLASMA IN THE SOUTH OF THE GALACTIC CENTER: A RELIC OF THE PAST GALACTIC CENTER ACTIVITY?

    SciTech Connect

    Nakashima, S.; Nobukawa, M.; Uchida, H.; Tanaka, T.; Tsuru, T. G.; Koyama, K.; Murakami, H.; Uchiyama, H.

    2013-08-10

    We report Suzaku results for soft X-ray emission to the south of the Galactic center (GC). The emission (hereafter {sup G}C South{sup )} has an angular size of {approx}42' Multiplication-Sign 16' centered at (l, b) {approx} (0. Degree-Sign 0, - 1. Degree-Sign 4) and is located in the largely extended Galactic ridge X-ray emission (GRXE). The X-ray spectrum of GC South exhibits emission lines from highly ionized atoms. Although the X-ray spectrum of the GRXE can be well fitted with a plasma in collisional ionization equilibrium (CIE), that of GC South cannot be fitted with a plasma in CIE, leaving hump-like residuals at {approx}2.5 and 3.5 keV, which are attributable to the radiative recombination continua of the K-shells of Si and S, respectively. In fact, GC South spectrum is well fitted with a recombination-dominant plasma model; the electron temperature is 0.46 keV while atoms are highly ionized (kT = 1.6 keV) in the initial epoch, and the plasma is now in a recombining phase at a relaxation scale (plasma density Multiplication-Sign elapsed time) of 5.3 Multiplication-Sign 10{sup 11} s cm{sup -3}. The absorption column density of GC South is consistent with that toward the GC region. Thus, GC South is likely to be located in the GC region ({approx}8 kpc distance). The size of the plasma, the mean density, and the thermal energy are estimated to be {approx}97 pc Multiplication-Sign 37 pc, 0.16 cm{sup -3}, and 1.6 Multiplication-Sign 10{sup 51} erg, respectively. We discuss possible origins of the recombination-dominant plasma as a relic of past activity in the GC region.

  13. Discovery of the Recombining Plasma in the South of the Galactic Center: A Relic of the Past Galactic Center Activity?

    NASA Astrophysics Data System (ADS)

    Nakashima, S.; Nobukawa, M.; Uchida, H.; Tanaka, T.; Tsuru, T. G.; Koyama, K.; Murakami, H.; Uchiyama, H.

    2013-08-01

    We report Suzaku results for soft X-ray emission to the south of the Galactic center (GC). The emission (hereafter "GC South") has an angular size of ~42' × 16' centered at (l, b) ~ (0.°0, - 1.°4) and is located in the largely extended Galactic ridge X-ray emission (GRXE). The X-ray spectrum of GC South exhibits emission lines from highly ionized atoms. Although the X-ray spectrum of the GRXE can be well fitted with a plasma in collisional ionization equilibrium (CIE), that of GC South cannot be fitted with a plasma in CIE, leaving hump-like residuals at ~2.5 and 3.5 keV, which are attributable to the radiative recombination continua of the K-shells of Si and S, respectively. In fact, GC South spectrum is well fitted with a recombination-dominant plasma model; the electron temperature is 0.46 keV while atoms are highly ionized (kT = 1.6 keV) in the initial epoch, and the plasma is now in a recombining phase at a relaxation scale (plasma density × elapsed time) of 5.3 × 1011 s cm-3. The absorption column density of GC South is consistent with that toward the GC region. Thus, GC South is likely to be located in the GC region (~8 kpc distance). The size of the plasma, the mean density, and the thermal energy are estimated to be ~97 pc × 37 pc, 0.16 cm-3, and 1.6 × 1051 erg, respectively. We discuss possible origins of the recombination-dominant plasma as a relic of past activity in the GC region.

  14. Modulation of the fluorescence yield in heliobacterial cells by induction of charge recombination in the photosynthetic reaction center.

    PubMed

    Redding, Kevin E; Sarrou, Iosifina; Rappaport, Fabrice; Santabarbara, Stefano; Lin, Su; Reifschneider, Kiera T

    2014-05-01

    Heliobacteria contain a very simple photosynthetic apparatus, consisting of a homodimeric type I reaction center (RC) without a peripheral antenna system and using the unique pigment bacteriochlorophyll (BChl) g. They are thought to use a light-driven cyclic electron transport pathway to pump protons, and thereby phosphorylate ADP, although some of the details of this cycle are yet to be worked out. We previously reported that the fluorescence emission from the heliobacterial RC in vivo was increased by exposure to actinic light, although this variable fluorescence phenomenon exhibited very different characteristics to that in oxygenic phototrophs (Collins et al. 2010). Here, we describe the underlying mechanism behind the variable fluorescence in heliobacterial cells. We find that the ability to stably photobleach P800, the primary donor of the RC, using brief flashes is inversely correlated to the variable fluorescence. Using pump-probe spectroscopy in the nanosecond timescale, we found that illumination of cells with bright light for a few seconds put them in a state in which a significant fraction of the RCs underwent charge recombination from P800 (+)A0 (-) with a time constant of ~20 ns. The fraction of RCs in the rapidly back-reacting state correlated very well with the variable fluorescence, indicating that nearly all of the increase in fluorescence could be explained by charge recombination of P800 (+)A0 (-), some of which regenerated the singlet excited state. This hypothesis was tested directly by time-resolved fluorescence studies in the ps and ns timescales. The major decay component in whole cells had a 20-ps decay time, representing trapping by the RC. Treatment of cells with dithionite resulted in the appearance of a ~18-ns decay component, which accounted for ~0.6 % of the decay, but was almost undetectable in the untreated cells. We conclude that strong illumination of heliobacterial cells can result in saturation of the electron acceptor pool

  15. Electron transfer kinetics in photosynthetic reaction centers embedded in trehalose glasses: trapping of conformational substates at room temperature.

    PubMed Central

    Palazzo, Gerardo; Mallardi, Antonia; Hochkoeppler, Alejandro; Cordone, Lorenzo; Venturoli, Giovanni

    2002-01-01

    We report on room temperature electron transfer in the reaction center (RC) complex purified from Rhodobacter sphaeroides. The protein was embedded in trehalose-water systems of different trehalose/water ratios. This enabled us to get new insights on the relationship between RC conformational dynamics and long-range electron transfer. In particular, we measured the kinetics of electron transfer from the primary reduced quinone acceptor (Q(A)(-)) to the primary photo oxidized donor (P(+)), by time-resolved absorption spectroscopy, as a function of the matrix composition. The composition was evaluated either by weighing (liquid samples) or by near infrared spectroscopy (highly viscous or solid glasses). Deconvolution of the observed, nonexponential kinetics required a continuous spectrum of rate constants. The average rate constant ( = 8.7 s(-1) in a 28% (w/w) trehalose solution) increases smoothly by increasing the trehalose/water ratio. In solid glasses, at trehalose/water ratios > or = 97%, an abrupt increase is observed ( = 26.6 s(-1) in the driest solid sample). A dramatic broadening of the rate distribution function parallels the above sudden increase. Both effects fully revert upon rehydration of the glass. We compared the kinetics observed at room temperature in extensively dried water-trehalose matrices with the ones measured in glycerol-water mixtures at cryogenic temperatures and conclude that, in solid trehalose-water glasses, the thermal fluctuations among conformational substates are inhibited. This was inferred from the large broadening of the rate constant distribution for electron transfer obtained in solid glasses, which was due to the free energy distribution barriers having become quasi static. Accordingly, the RC relaxation from dark-adapted to light-adapted conformation, which follows primary charge separation at room temperature, is progressively hindered over the time scale of P(+)Q(A)(-) charge recombination, upon decreasing the

  16. Barriers to physical activity in an on-site corporate fitness center.

    PubMed

    Schwetschenau, Heather M; O'Brien, William H; Cunningham, Christopher J L; Jex, Steve M

    2008-10-01

    Many corporations provide employees the option of participating in on-site fitness centers, but utilization rates are low. Perceived barriers to physical activity have been established as important correlates of physical activity, and recent research indicates that barriers may vary across settings. Work-site fitness centers may present unique barriers to participation, but there are currently no standardized measures that assess such barriers. Eighty-eight employees of a midwestern corporation completed a survey designed to identify and evaluate the extent to which barriers influence participation in an on-site corporate fitness center. Regression analyses revealed that external environmental barriers (e.g., inadequate exercise facilities) significantly accounted for not joining the fitness center, and for decreased duration of visits to the facility among members. Internal barriers (e.g., feeling embarrassed to exercise around coworkers) significantly accounted for frequency of fitness center visits among members. This corporate specific measure may lead to more effective interventions aimed to increase use of on-site corporate fitness centers.

  17. Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

    DOEpatents

    Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

    2010-08-03

    A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

  18. Luminescence induced by dehydration of kaolin - Association with electron-spin-active centers and with surface activity for dehydration-polymerization of glycine

    NASA Technical Reports Server (NTRS)

    Coyne, L.; Hovatter, W.; Sweeney, M.

    1983-01-01

    Experimental data concerning emission of light upon dehydration as a function of preheating and pre-gamma-irradiation are correlated with reported studies of electron-spin resonance (ESR) activity after similar pretreatments. The effect of these pretreatments on the kaolin-promoted incorporation of glycine into peptide oligomers in a wet/cold, hot/dry fluctuating environment is compared to their effect on the ESR and luminescent signals. The existence of spectroscopically active centers appears to be loosely anticorrelated with reaction yield; these yields are increased by increasing the overall energy content of the material. It is concluded that some part of the chemical yield is produced by a mechanism involving intrinsic, excited electronic states of the clay crystal lattice. These states may be derived from thermally, interfacially, and/or mechanically induced charge reorganization within interspersed energy levels in the band structure of the material.

  19. Greenhouse gas (GHG) mitigation technology performance: Activities of the GHG Technology Verification Center. Report for November 1997--September 1998

    SciTech Connect

    Piccot, S.D.; Kirchgessner, D.A.

    1998-12-31

    The paper describes the Greenhouse Gas (GHG) Technology Verification Center`s mission, operational characteristics, and current activities in the natural gas industry, solid waste landfill industry, energy industries, and microelectronics industry. It also outlines the Center`s future plans and gives results of a recent phosphoric acid fuel cell verification at two landflls in the US. It describes how technology vendors, developers, users, and others can utilize the Center`s testing, analysis, and outreach activities and outlines the types of technologies planned for testing over the next 3 to 5 years.

  20. New tetragonal form of reaction centers from Rhodobacter sphaeroides and the involvement of a manganese ion at a crystal contact point.

    PubMed

    Uyeda, G; Cámara-Artigas, A; Williams, J C; Allen, J P

    2005-08-01

    Crystals have been obtained of wild-type reaction centers from Rhodobacter sphaeroides using manganese chloride as a precipitating agent. The crystals belong to the tetragonal space group P4(2)22, with unit-cell parameters a = b = 207.8, c = 107.5 A. The crystal structure has been determined to a resolution limit of 4.6 A using a previously determined structure of the reaction center as a molecular-replacement model. The calculated electron-density maps show the presence of a manganese ion at one of the crystal contact points bridging two symmetry-related histidine residues, suggesting that the metal plays a key role in facilitating the crystallization of the protein in this form.

  1. Modeling the quinone-B binding site of the photosystem-II reaction center using notions of complementarity and contact-surface between atoms.

    PubMed

    Sobolev, V; Edelman, M

    1995-03-01

    Functional identity and significant similarities in cofactors and sequence exist between the L and M reaction center proteins of the photosynthetic bacteria and the D1 and D2 photosystem-II reaction center proteins of cyanobacteria, algae, and plants. A model of the quinone (QB) binding site of the D1 protein is presented based upon the resolved structure of the QB binding pocket of the L subunit, and introducing novel quantitative notions of complementarity and contact surface between atoms. This model, built without using traditional methods of molecular mechanics and restricted to residues in direct contact with QB, accounts for the experimentally derived functional state of mutants of the D1 protein in the region of QB. It predicts the binding of both the classical and phenol-type PSII herbicides and rationalizes the relative levels of tolerance of mutant phenotypes.

  2. A Mesoporous Indium Metal-Organic Framework: Remarkable Advances in Catalytic Activity for Strecker Reaction of Ketones.

    PubMed

    Reinares-Fisac, Daniel; Aguirre-Díaz, Lina María; Iglesias, Marta; Snejko, Natalia; Gutiérrez-Puebla, Enrique; Monge, M Ángeles; Gándara, Felipe

    2016-07-27

    With the aim of developing new highly porous, heterogeneous Lewis acid catalysts for multicomponent reactions, a new mesoporous metal-organic framework, InPF-110 ([In3O(btb)2(HCOO)(L)], (H3btb = 1,3,5-tris(4-carboxyphenyl)benzene acid, L = methanol, water, or ethanol), has been prepared with indium as the metal center. It exhibits a Langmuir surface area of 1470 m(2) g(-1), and its structure consists of hexagonal pores with a 2.8 nm aperture, which allows the diffusion of multiple substrates. This material presents a large density of active metal sites resulting in outstanding catalytic activity in the formation of substituted α-aminonitriles through the one-pot Strecker reaction of ketones. In this respect, InPF-110 stands out compared to other catalysts for this reaction due to the small catalyst loadings required, and without the need for heat or solvents. Furthermore, X-ray single crystal diffraction studies clearly show the framework-substrate interaction through coordination to the accessible indium sites.

  3. Boron-doped graphene as promising support for platinum catalyst with superior activity towards the methanol electrooxidation reaction

    NASA Astrophysics Data System (ADS)

    Sun, Yongrong; Du, Chunyu; An, Meichen; Du, Lei; Tan, Qiang; Liu, Chuntao; Gao, Yunzhi; Yin, Geping

    2015-12-01

    We report the synthesis of boron-doped graphene by thermally annealing the mixture of graphene oxide and boric acid, and its usage as the support of Pt catalyst towards the methanol oxidation reaction. The composition, structure and morphology of boron-doped graphene and its supported Pt nanoparticles (Pt/BG) are characterized by transmission electron microscopy, inductively coupled plasma mass spectrometry, Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy. It is revealed that boron atoms are doped into graphene network in the form of BC2O and BCO2 bonds, which lead to the increase in defect sites and facilitate the subsequent deposition of Pt nanoparticles. Therefore, the Pt/BG catalyst presents smaller particle size and narrower size distribution than the graphene supported Pt (Pt/G) catalyst. When evaluated as the electrocatalyst for the methanol oxidation reaction, the Pt/BG catalyst exhibits excellent electrochemical activity and stability demonstrated by cyclic voltammetry and chronoamperometry tests. The enhanced activity is mainly ascribed to the electronic interaction between boron-doped graphene and Pt nanoparticles, which lowers the d-band center of Pt and thus weakens the absorption of the poisoning intermediate CO. Our work provides an alternative approach of improving the reaction kinetics for the oxidation of small organic molecules.

  4. Nucleophilic substitution at centers other than carbon: reaction at the chlorine of N-chloroacetanilides with triethylamine as the nucleophile

    SciTech Connect

    Underwood, G.R.; Dietze, P.E.

    1984-12-28

    The reaction between triethylamine (TEA) and a series of para-substituted N-chloroacetanilides has been studied in aqueous solution buffered to pHs between 1 and 5. The exclusive product derived from the aromatic moiety is the corresponding acetanilide. The reaction occurs via two parallel pseudo-second-order paths, one acid catalyzed (the Orton-like mechanism), the other uncatalyzed. The uncatalyzed reaction is accelerated by the presence of electron-withdrawing substituents on the aromatic ring and can best be represented as nucleophilic displacement at chlorine. It therefore appears to be the prototype of a convenient class of reactions for the study of displacement reactions at chlorine. The rho value for this reaction is 3.87, indicating substantial negative charge buildup in the aromatic ring during of the transition state. The acid-catalyzed reaction is more complex, presumable involving a protonation equilibrium for the N-chloroacetanilide prior to the rate-determining step similar to that in the Orton reaction. 15 references, 2 figures, 3 tables.

  5. Digallane with redox-active diimine ligand: dualism of electron-transfer reactions.

    PubMed

    Fedushkin, Igor L; Skatova, Alexandra A; Dodonov, Vladimir A; Chudakova, Valentina A; Bazyakina, Natalia L; Piskunov, Alexander V; Demeshko, Serhiy V; Fukin, Georgy K

    2014-05-19

    The reactivity of digallane (dpp-Bian)Ga-Ga(dpp-Bian) (1), which consists of redox-active ligand 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-Bian), has been studied. The reaction of 1 with I2 proceeds via one-electron oxidation of each of two dpp-Bian ligands to a radical-anionic state and affords complex (dpp-Bian)IGa-GaI(dpp-Bian) (2). Dissolution of complex 2 in pyridine (Py) gives monomeric compound (dpp-Bian)GaI(Py) (3) as a result of a solvent-induced intramolecular electron transfer from the metal-metal bond to the dpp-Bian ligands. Treatment of compound 3 with B(C6F5)3 leads to removal of pyridine and restores compound 2. The reaction of compound 1 with 3,6-di-tert-butyl-ortho-benzoquinone (3,6-Q) proceeds with oxidation of all the redox-active centers in 1 (the Ga-Ga bond and two dpp-Bian dianions) and results in mononuclear catecholate (dpp-Bian)Ga(Cat) (4) (Cat = [3,6-Q](2-)). Treatment of 4 with AgBF4 gives a mixture of [(dpp-Bian)2Ag][BF4] (5) and (dpp-Bian)GaF(Cat) (6), which both consist of neutral dpp-Bian ligands. The reduction of benzylideneacetone (BA) with 1 generates the BA radical-anions, which dimerize, affording (dpp-Bian)Ga-(BA-BA)-Ga(dpp-Bian) (7). In this case the Ga-Ga bond remains unchanged. Within 10 min at 95 °C in solution compound 7 undergoes transformation to paramagnetic complex (dpp-Bian)Ga(BA-BA) (8) and metal-free compound C36H40N2 (9). The latter is a product of intramolecular addition of the C-H bond of one of the iPr groups to the C═N bond in dpp-Bian. Diamagnetic compounds 3, 5, 6, and 9 have been characterized by NMR spectroscopy, and paramagnetic complexes 2, 4, 7, and 8 by ESR spectroscopy. Molecular structures of 2-7 and 9 have been established by single-crystal X-ray analysis.

  6. Activation energy for a model ferrous-ferric half reaction from transition path sampling

    NASA Astrophysics Data System (ADS)

    Drechsel-Grau, Christof; Sprik, Michiel

    2012-01-01

    Activation parameters for the model oxidation half reaction of the classical aqueous ferrous ion are compared for different molecular simulation techniques. In particular, activation free energies are obtained from umbrella integration and Marcus theory based thermodynamic integration, which rely on the diabatic gap as the reaction coordinate. The latter method also assumes linear response, and both methods obtain the activation entropy and the activation energy from the temperature dependence of the activation free energy. In contrast, transition path sampling does not require knowledge of the reaction coordinate and directly yields the activation energy [C. Dellago and P. G. Bolhuis, Mol. Simul. 30, 795 (2004), 10.1080/08927020412331294869]. Benchmark activation energies from transition path sampling agree within statistical uncertainty with activation energies obtained from standard techniques requiring knowledge of the reaction coordinate. In addition, it is found that the activation energy for this model system is significantly smaller than the activation free energy for the Marcus model, approximately half the value, implying an equally large entropy contribution.

  7. Atmospheric chemistry of the reaction ClO + O2 reversible reaction ClO (center dot) O2: Where it stands, what needs to be done, and why?

    NASA Technical Reports Server (NTRS)

    Prasad, Sheo S.; Lee, Timothy J.

    1994-01-01

    Possible existence and chemistry of ClO (center dot) O2 was originally proposed to explain the Norrish-Neville effect that O2 suppresses chlorine photosensitized loss of ozone. It was also thought that ClO (center dot) O2 might have some atmospheric chemistry significance. Recently, doubts have been cast on this proposal, because certain laboratory data seem to imply that the equilibrium constant of the title reaction is so small that ClO (center dot) O2 may be too unstable to matter. However, those data create only a superficial illusion to that effect, because on a closer analysis they do not disprove a moderately stable and chemically significant ClO (center dot) O2. Furthermore, our state-of-the-science accurate computational chemistry calculations also suggest that ClO (center dot) O2 may be a weakly bound ClOOO radical with a reactive (2)A ground electronic state. There is therefore a need to design and perform definitive experimental tests of the existence and chemistry of the ClO (center dot) O2 species, which we discuss and which have the potential to mediate the chlorine-catalyzed stratospheric ozone depletion.

  8. Methandiide as a non-innocent ligand in carbene complexes: from the electronic structure to bond activation reactions and cooperative catalysis.

    PubMed

    Becker, Julia; Modl, Tanja; Gessner, Viktoria H

    2014-09-01

    The synthesis of a ruthenium carbene complex based on a sulfonyl-substituted methandiide and its application in bond activation reactions and cooperative catalysis is reported. In the complex, the metal-carbon interaction can be tuned between a Ru-C single bond with additional electrostatic interactions and a Ru=C double bond, thus allowing the control of the stability and reactivity of the complex. Hence, activation of polar and non-polar bonds (O-H, H-H) as well as dehydrogenation reactions become possible. In these reactions the carbene acts as a non-innocent ligand supporting the bond activation as nucleophilic center in the 1,2-addition across the metal-carbon double bond. This metal-ligand cooperativity can be applied in the catalytic transfer hydrogenation for the reduction of ketones. This concept opens new ways for the application of carbene complexes in catalysis.

  9. Understanding the role of gold nanoparticles in enhancing the catalytic activity of manganese oxides in water oxidation reactions.

    PubMed

    Kuo, Chung-Hao; Li, Weikun; Pahalagedara, Lakshitha; El-Sawy, Abdelhamid M; Kriz, David; Genz, Nina; Guild, Curtis; Ressler, Thorsten; Suib, Steven L; He, Jie

    2015-02-16

    The Earth-abundant and inexpensive manganese oxides (MnOx) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnOx catalysts are still much lower than that of nanostructured IrO2 and RuO2 catalysts. Herein, we demonstrate that doping MnOx polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnOx/AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn(3+) species, a small amount of AuNPs (<5%) in α-MnO2/AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure α-MnO2.

  10. Parallel electron donation pathways to cytochrome c(z) in the type I homodimeric photosynthetic reaction center complex of Chlorobium tepidum.

    PubMed

    Tsukatani, Yusuke; Azai, Chihiro; Kondo, Toru; Itoh, Shigeru; Oh-Oka, Hirozo

    2008-09-01

    We studied the regulation mechanism of electron donations from menaquinol:cytochrome c oxidoreductase and cytochrome c-554 to the type I homodimeric photosynthetic reaction center complex of the green sulfur bacterium Chlorobium tepidum. We measured flash-induced absorption changes of multiple cytochromes in the membranes prepared from a mutant devoid of cytochrome c-554 or in the reconstituted membranes by exogenously adding cytochrome c-555 purified from Chlorobium limicola. The results indicated that the photo-oxidized cytochrome c(z) bound to the reaction center was rereduced rapidly by cytochrome c-555 as well as by the menaquinol:cytochrome c oxidoreductase and that cytochrome c-555 did not function as a shuttle-like electron carrier between the menaquinol:cytochrome c oxidoreductase and cytochrome c(z). It was also shown that the rereduction rate of cytochrome c(z) by cytochrome c-555 was as high as that by the menaquinol:cytochrome c oxidoreductase. The two electron-transfer pathways linked to sulfur metabolisms seem to function independently to donate electrons to the reaction center.

  11. Titanium oxynitride interlayer to influence oxygen reduction reaction activity and corrosion stability of Pt and Pt-Ni alloy.

    PubMed

    Tan, XueHai; Wang, Liya; Zahiri, Beniamin; Kohandehghan, Alireza; Karpuzov, Dimitre; Lotfabad, Elmira Memarzadeh; Li, Zhi; Eikerling, Michael H; Mitlin, David

    2015-01-01

    A key advancement target for oxygen reduction reaction catalysts is to simultaneously improve both the electrochemical activity and durability. To this end, the efficacy of a new highly conductive support that comprises of a 0.5 nm titanium oxynitride film coated by atomic layer deposition onto an array of carbon nanotubes has been investigated. Support effects for pure platinum and for a platinum (50 at %)/nickel alloy have been considered. Oxynitride induces a downshift in the d-band center for pure platinum and fundamentally changes the platinum particle size and spatial distribution. This results in major enhancements in activity and corrosion stability relative to an identically synthesized catalyst without the interlayer. Conversely, oxynitride has a minimal effect on the electronic structure and microstructure, and therefore, on the catalytic performance of platinum-nickel. Calculations based on density functional theory add insight with regard to compositional segregation that occurs at the alloy catalyst-support interface.

  12. Nutrition and Physical Activity Practices in Childcare Centers versus Family Childcare Homes

    ERIC Educational Resources Information Center

    Natale, Ruby; Page, Monica; Sanders, Lee

    2014-01-01

    Obesity rates among preschool-aged children have doubled in the past 10 years, and 60% of these children spend the majority of their day in childcare facilities. Few studies have examined the quality of nutrition and physical activity practices in childcare centers as compared to family childcare homes. The purpose of this study is to determine if…

  13. Structures of glycosylated mammalian glutaminyl cyclases reveal conformational variability near the active center.

    PubMed

    Ruiz-Carrillo, David; Koch, Birgit; Parthier, Christoph; Wermann, Michael; Dambe, Tresfore; Buchholz, Mirko; Ludwig, Hans-Henning; Heiser, Ulrich; Rahfeld, Jens-Ulrich; Stubbs, Milton T; Schilling, Stephan; Demuth, Hans-Ulrich

    2011-07-19

    Formation of N-terminal pyroglutamate (pGlu or pE) from glutaminyl or glutamyl precursors is catalyzed by glutaminyl cyclases (QC). As the formation of pGlu-amyloid has been linked with Alzheimer's disease, inhibitors of QCs are currently the subject of intense development. Here, we report three crystal structures of N-glycosylated mammalian QC from humans (hQC) and mice (mQC). Whereas the overall structures of the enzymes are similar to those reported previously, two surface loops in the neighborhood of the active center exhibit conformational variability. Furthermore, two conserved cysteine residues form a disulfide bond at the base of the active center that was not present in previous reports of hQC structure. Site-directed mutagenesis suggests a structure-stabilizing role of the disulfide bond. At the entrance to the active center, the conserved tryptophan residue, W(207), which displayed multiple orientations in previous structure, shows a single conformation in both glycosylated human and murine QCs. Although mutagenesis of W(207) into leucine or glutamine altered substrate conversion significantly, the binding constants of inhibitors such as the highly potent PQ50 (PBD150) were minimally affected. The crystal structure of PQ50 bound to the active center of murine QC reveals principal binding determinants provided by the catalytic zinc ion and a hydrophobic funnel. This study presents a first comparison of two mammalian QCs containing typical, conserved post-translational modifications.

  14. Individual Information-Centered Approach for Handling Physical Activity Missing Data

    ERIC Educational Resources Information Center

    Kang, Minsoo; Rowe, David A.; Barreira, Tiago V.; Robinson, Terrance S.; Mahar, Matthew T.

    2009-01-01

    The purpose of this study was to validate individual information (II)-centered methods for handling missing data, using data samples of 118 middle-aged adults and 91 older adults equipped with Yamax SW-200 pedometers and Actigraph accelerometers for 7 days. We used a semisimulation approach to create six data sets: three physical activity outcome…

  15. Research and technology activities at Ames Research Center's Biomedical Research Division

    NASA Technical Reports Server (NTRS)

    Martello, N.

    1985-01-01

    Various research and technology activities at Ames Research Center's Biomedical Research Division are described. Contributions to the Space Administration's goals in the life sciences include descriptions of research in operational medicine, cardiovascular deconditioning, motion sickness, bone alterations, muscle atrophy, fluid and electrolyte changes, radiation effects and protection, behavior and performance, gravitational biology, and life sciences flight experiments.

  16. Activating Community Health Center Patients in Developing Question-Formulation Skills: A Qualitative Study

    ERIC Educational Resources Information Center

    Lu, Wei-Hsin; Deen, Darwin; Rothstein, Dan; Santana, Luz; Gold, Marthe R.

    2011-01-01

    The authors developed and delivered a brief patient activation intervention (PAI) that sought to facilitate physician-patient communication. The intervention was designed to assist low-income, racial/ethnic minority users of community health centers in building skills and confidence asking questions. The PAI takes 8 to 10 minutes to deliver and…

  17. Significant Centers of Tectonic Activity as Identified by Wrinkle Ridges for the Western Hemisphere of Mars

    NASA Technical Reports Server (NTRS)

    Anderson, R.C.; Haldemann, A. F. C.; Golombek, M. P.; Franklin, B. J.; Dohm, J. M.; Lias, J.

    2000-01-01

    The western hemisphere region of Mars has been the site of numerous scientific investigations regarding its tectonic evolution. For this region of Mars, the dominant tectonic region is the Tharsis province. Tharsis is characterized by an enormous system of radiating grabens and a circumferential system of wrinkle ridges. Past investigations of grabens associated with Tharsis have identified specific centers of tectonic activity. A recent structural analysis of the western hemisphere region of Mars which includes the Tharsis region, utilized 25,000 structures to determine the history of local and regional centers of tectonic activity based primarily on the spatial and temporal relationships of extensional features. This investigation revealed that Tharsis is more structurally complex (heterogeneous) than has been previously identified: it consists of numerous regional and local centers of tectonic activity (some are more dominant and/or more long lived than others). Here we use the same approach as Anderson et al. to determine whether the centers of tectonic activity that formed the extensional features also contributed to wrinkle ridge (compressional) formation.

  18. Can Physical Education and Physical Activity Outcomes Be Developed Simultaneously Using a Game-Centered Approach?

    ERIC Educational Resources Information Center

    Miller, Andrew; Christensen, Erin; Eather, Narelle; Gray, Shirley; Sproule, John; Keay, Jeanne; Lubans, David

    2016-01-01

    The primary objective of this study was to evaluate the efficacy of a pilot intervention using a game-centered approach for improvement of physical activity (PA) and physical education (PE) outcomes simultaneously, and if this had an impact on enjoyment of PE. A group-randomized controlled trial with a 7-week wait-list control group was conducted…

  19. Students´ Perspectives on eLearning Activities in Person-Centered, Blended Learning Settings

    ERIC Educational Resources Information Center

    Haselberger, David; Motsching, Renate

    2016-01-01

    Blended or hybrid learning has become a frequent practice in higher education. In this article our primary research interest was to find out how students perceived eLearning activities in blended learning courses based on the person-centered paradigm. Through analyzing the content of a series of semi-structured interviews we found out that…

  20. View of activity in Mission Control Center during Apollo 15 lunar landing

    NASA Technical Reports Server (NTRS)

    1971-01-01

    An overall, wide-angle lens view of activity in the Mission Operations Control Room in the Mission Control Center during the landing of the Apollo 15 Lunar Module (LM) on the Moon. The LM 'Falcon' touched down on the lunar surface at ground elapsed time of 104 hours 42 minutes 29 seconds.

  1. The function of the earth observing system - Data information system Distributed Active Archive Centers

    NASA Technical Reports Server (NTRS)

    Lapenta, C. C.

    1992-01-01

    The functionality of the Distributed Active Archive Centers (DAACs) which are significant elements of the Earth Observing System Data and Information System (EOSDIS) is discussed. Each DAAC encompasses the information management system, the data archival and distribution system, and the product generation system. The EOSDIS DAACs are expected to improve the access to earth science data set needed for global change research.

  2. Thermal Technology Development Activities at the Goddard Space Flight Center - 2001

    NASA Technical Reports Server (NTRS)

    Butler, Dan

    2002-01-01

    This presentation provides an overview of thermal technology development activities carried out at NASA's Goddard Space Flight Center during 2001. Specific topics covered include: two-phase systems (heat pipes, capillary pumped loops, vapor compression systems and phase change materials), variable emittance systems, advanced coatings, high conductivity materials and electrohydrodynamic (EHD) thermal coatings. The application of these activities to specific space missions is also discussed.

  3. Paris Observatory Analysis Center (OPAR): Report on Activities, January - December 2012

    NASA Technical Reports Server (NTRS)

    Lambert, Sebastien; Barache, Christophe

    2013-01-01

    We report on activities of the Paris Observatory VLBI Analysis Center (OPAR) for calendar year 2012 concerning the development of operational tasks, the development of our Web site, and various other activities: monitoring of the Earth's free core nutation, measuring of the post-seismic displacements of some stations, and the analysis of the recent IVS R&D sessions, including observations of quasars close to the Sun.

  4. Analysis of ground reaction force and electromyographic activity of the gastrocnemius muscle during double support.

    PubMed

    Sousa, Andreia S P; Santos, Rubim; Oliveira, Francisco P M; Carvalho, Paulo; Tavares, João Manuel R S

    2012-05-01

    Mechanisms associated with energy expenditure during gait have been extensively researched and studied. According to the double-inverted pendulum model energy expenditure is higher during double support, as lower limbs need to work to redirect the centre of mass velocity. This study looks into how the ground reaction force of one limb affects the muscle activity required by the medial gastrocnemius of the contralateral limb during step-to-step transition. Thirty-five subjects were monitored as to the medial gastrocnemius electromyographic activity of one limb and the ground reaction force of the contralateral limb during double support. After determination of the Pearson correlation coefficient (r), a moderate correlation was observed between the medial gastrocnemius electromyographic activity of the dominant leg and the vertical (Fz) and anteroposterior (Fy) components of ground reaction force of the non-dominant leg (r = 0.797, p < 0.000 1; r = -0.807, p < 0.000 1). A weak and moderate correlation was observed between the medial gastrocnemius electromyographic activity of the non-dominant leg and the Fz and Fy of the dominant leg, respectively (r = 0.442, p = 0.018; r = -0.684 p < 0.000 1). The results obtained suggest that during double support, ground reaction force is associated with the electromyographic activity of the contralateral medial gastrocnemius and that there is an increased dependence between the ground reaction force of the non-dominant leg and the electromyographic activity of the dominant medial gastrocnemius.

  5. Catalytic activation of carbohydrates as formaldehyde equivalents for Stetter reaction with enones.

    PubMed

    Zhang, Junmin; Xing, Chong; Tiwari, Bhoopendra; Chi, Yonggui Robin

    2013-06-05

    We disclose the first catalytic activation of carbohydrates as formaldehyde equivalents to generate acyl anions as one-carbon nucleophilic units for a Stetter reaction. The activation involves N-heterocyclic carbene (NHC)-catalyzed C-C bond cleavage of carbohydrates via a retro-benzoin-type process to generate the acyl anion intermediates. This Stetter reaction constitutes the first success in generating formal formaldehyde-derived acyl anions as one-carbon nucleophiles for non-self-benzoin processes. The renewable nature of carbohydrates, accessible from biomass, further highlights the practical potential of this fundamentally interesting catalytic activation.

  6. ACTIVE: a program to calculate and plot reaction rates from ANISN calculated fluxes

    SciTech Connect

    Judd, J.L.

    1981-12-01

    The ACTIVE code calculates spatial heating rates, tritium production rates, neutron reaction rates, and energy spectra from particle fluxes calculated by ANISN. ACTIVE has a variety of input options including the capability to plot all calculated spatial distributions. The code was primarily designed for use with fusion first wall/blanket systems, but could be applied to any one-dimensional problem.

  7. Mechanism of a C-H bond activation reaction in room-temperature alkane solution

    SciTech Connect

    Bromberg, S.E.; Yang, H.; Asplund, M.C.

    1997-10-10

    Chemical reactions that break alkane carbon-hydrogen (C-H) bonds are normally carried out under conditions of high temperature and pressure because these bonds are extremely strong ({approx} 100 kilocalories per mole), but certain metal complexes can activate C-H bonds in alkane solution under the mild conditions of room temperature and pressure. Time-resolved infrared experiments probing the initial femtosecond dynamics through the nano- and microsecond kinetics to the final stable products have been used to generate a detailed picture of the C-H activation reaction. Structures of all of the intermediates involved in the reaction of Tp*Rh(CO){sub 2} (Tp* = HB-Pz{sub 3}*, Pz* = 3,5-di-methylpyrazolyl) in alkane solution have been identified and assigned, and energy barriers for each reaction step from solvation to formation of the final alkyl hydride product have been estimated from transient lifetimes. 27 refs., 6 figs.

  8. The mechanism of a C-H Bond Activation reaction in roomtemperature alkane solution

    SciTech Connect

    Bromberg, Steven E.; Yang, Haw; Asplund, Matthew C.; Lian, T.; McNamara, B.K.; Kotz, K.T.; Yeston, J.S.; Wilkens, M.; Frei, H.; Bergman,Robert G.; Harris, C.B.

    1997-07-31

    Chemical reactions that break alkane carbon-hydrogen (C-H) bonds are normally carried out under conditions of high temperature and pressure because these bonds are extremely strong ({approx}100 kilocalories per mole), but certain metal complexes can activate C-H bonds in alkane solution under the mild conditions of room temperature and pressure. Time-resolved infrared experiments probing the initial femtosecond dynamics through the nano- and microsecond kinetics to the final stable products have been used to generate a detailed picture of the C-H activation reaction. Structures of all of the intermediates involved in the reaction of Tp*Rh(CO)2 (Tp* = HB-Pz3*, Pz* = 3,5-dimethylpyrazolyl) in alkane solution have been identified and assigned, and energy barriers for each reaction step from solvation to formation of the final alkylhydride product have been estimated from transient lifetimes.

  9. Center for Multiscale Plasma Dynamics: Report on Activities (UCLA/MIT), 2009-2010

    SciTech Connect

    Troy Carter

    2011-04-18

    The final 'phaseout' year of the CMPD ended July 2010; a no cost extension was requested until May 2011 in order to enable the MIT subcontract funds to be fully utilized. Research progress over this time included verification and validation activities for the BOUT and BOUT++ code, studies of spontaneous reconnection in the VTF facility at MIT, and studies of the interaction between Alfven waves and drift waves in LAPD. The CMPD also hosted the 6th plasma physics winter school in 2010 (jointly with the NSF frontier center the Center for Magnetic Self-Organization, significant funding came from NSF for this most recent iteration of the Winter School).

  10. Solvent-Induced Reversal of Activities between Two Closely Related Heterogeneous Catalysts in the Aldol Reaction

    SciTech Connect

    Kandel, Kapil; Althaus, Stacey M; Peeraphatdit, Chorthip; Kobayashi, Takeshi; Trewyn, Brian G; Pruski, Marek; Slowing, Igor I

    2013-01-11

    The relative rates of the aldol reaction catalyzed by supported primary and secondary amines can be inverted by 2 orders of magnitude, depending on the use of hexane or water as a solvent. Our analyses suggest that this dramatic shift in the catalytic behavior of the supported amines does not involve differences in reaction mechanism, but is caused by activation of imine to enamine equilibria and stabilization of iminium species. The effects of solvent polarity and acidity were found to be important to the performance of the catalytic reaction. This study highlights the critical role of solvent in multicomponent heterogeneous catalytic processes.

  11. Organocatalytic Michael and Friedel-Crafts reactions in enantioselective synthesis of biologically active compounds

    NASA Astrophysics Data System (ADS)

    Maltsev, O. V.; Beletskaya, Irina P.; Zlotin, Sergei G.

    2011-11-01

    Recent applications of organocatalytic Michael and Friedel-Crafts reactions in enantioselective synthesis of biologically active compounds: natural products, pharmaceutical agents and plant protection agents are reviewed. The key mechanisms of stereoinduction, types of organocatalysts and reagents used in these reactions are considered. The material is classified according to the type of newly formed bonds incorporating the asymmetric carbon atom, and the information for the most numerous C-C coupling reactions is systematized according to the natures of the electrophile and the nucleophile. The bibliography includes 433 references. Dedicated to Academician O M Nefedov on the occasion of his 80th birthday.

  12. Acridine orange staining reaction as an index of physiological activity in Escherichia coli

    NASA Technical Reports Server (NTRS)

    McFeters, G. A.; Singh, A.; Byun, S.; Callis, P. R.; Williams, S.

    1991-01-01

    The assumption that the acridine orange (AO) color reaction may be used as an index of physiological activity was investigated in laboratory grown Escherichia coli. Spectrofluorometric observations of purified nucleic acids, ribosomes and the microscopic color of bacteriophage-infected cells stained with AO confirmed the theory that single-stranded nucleic acids emit orange to red fluorescence while those that are double-stranded fluoresce green in vivo. Bacteria growing actively in a rich medium could be distinguished from cells in stationary phase by the AO reaction. Cells from log phase appeared red, whereas those in stationary phase were green. However, this differentiation was not seen when the bacteria were grown in a minimal medium or when a variation of the staining method was used. Also, shifting bacteria in stationary phase to starvation conditions rapidly changed their AO staining reaction. Boiling and exposure to lethal concentrations of azide and formalin resulted in stationary-phase cells that appeared red after staining but bacteria killed with chlorine remained green. These findings indicate that the AO staining reaction may be suggestive of physiological activity under defined conditions. However, variables in staining and fixation procedures as well as uncertainties associated with mixed bacterial populations in environmental samples may produce results that are not consistent with the classical interpretation of this reaction. The importance of validating the putative physiological implications of this staining reaction is stressed.

  13. Earth Science Data Archive and Access at the NASA/Goddard Space Flight Center Distributed Active Archive Center (DAAC)

    NASA Technical Reports Server (NTRS)

    Leptoukh, Gregory

    1999-01-01

    The Goddard Distributed Active Archive Center (DAAC), as an integral part of the Earth Observing System Data and Information System (EOSDIS), is the official source of data for several important earth remote sensing missions. These include the Sea-viewing Wide-Field-of-view Sensor (SeaWiFS) launched in August 1997, the Tropical Rainfall Measuring Mission (TRMM) launched in November 1997, and the Moderate Resolution Imaging Spectroradiometer (MODIS) scheduled for launch in mid 1999 as part of the EOS AM-1 instrumentation package. The data generated from these missions supports a host of users in the hydrological, land biosphere and oceanographic research and applications communities. The volume and nature of the data present unique challenges to an Earth science data archive and distribution system such as the DAAC. The DAAC system receives, archives and distributes a large number of standard data products on a daily basis, including data files that have been reprocessed with updated calibration data or improved analytical algorithms. A World Wide Web interface is provided allowing interactive data selection and automatic data subscriptions as distribution options. The DAAC also creates customized and value-added data products, which allow additional user flexibility and reduced data volume. Another significant part of our overall mission is to provide ancillary data support services and archive support for worldwide field campaigns designed to validate the results from the various satellite-derived measurements. In addition to direct data services, accompanying documentation, WWW links to related resources, support for EOSDIS data formats, and informed response to inquiries are routinely provided to users. The current GDAAC WWW search and order system is being restructured to provide users with a simplified, hierarchical access to data. Data Browsers have been developed for several data sets to aid users in ordering data. These Browsers allow users to specify

  14. Drug reaction with eosinophilia and systemic symptoms (DRESS) and its relation with autoimmunity in a reference center in Mexico*

    PubMed Central

    Matta, Juan Manuel Ruiz; Flores, Silvia Méndez; Cherit, Judith Domínguez

    2017-01-01

    BACKGROUND Drug reaction with eosinophilia and systemic symptoms is a severe adverse drug reaction, with a reported mortality of 10%. Long-term outcomes involve organic failure and autoimmune diseases in some populations. OBJECTIVE To evaluate the clinical prognosis of patients with drug reaction with eosinophilia and systemic symptoms. METHODS We conducted a retrospective review at a referral hospital in Mexico City in a period of 22 years (1992-2013), looking up for records with diagnosis of DRESS according to RegiSCAR criteria. Clinical characteristics, organ failures, culprit drugs, treatment, and short and long-term sequelae were analyzed. RESULTS We found 11 patients with diagnosis of drug reaction with eosinophilia and systemic symptoms syndrome, 7 female and 4 male, with a median age of 22 years-old; 9 had maculopapular rash and 2 were erythrodermic. Affected organs were liver (8/11), kidney (6/11) and hematologic disorders (8/11). The most common culprit drugs were antiepileptic (63%). Systemic corticosteroids were given to 8 patients, being pyelonephritis (1/8) and pneumonia (2/8) the adverse events of this therapy. Long-term sequelae were 1 patient with renal failure, 1 patient with chronic anemia; and 2 patients developed autoimmune diseases (one autoimmune thyroid disease and another one with autoimmune thyroid disease and autoimmune hemolytic anemia). Study limitations: The retrospective nature of the study and the limited number of patients with drug reaction with eosinophilia and systemic symptoms. CONCLUSIONS Drug reaction with eosinophilia and systemic symptoms syndrome has been linked to the development of chronic organ failure. We found two young patients who developed autoimmune diseases in the short term. Patients with drug reaction with eosinophilia and systemic symptoms should have a long-term monitoring for signs or symptoms suggestive of an autoimmune disease. PMID:28225953

  15. Activities in the Spacelab Payload Operations Control Center (SL POCC) During the STS-42 IML-1

    NASA Technical Reports Server (NTRS)

    1992-01-01

    The primary payload for Space Shuttle Mission STS-42, launched January 22, 1992, was the International Microgravity Laboratory-1 (IML-1), a pressurized manned Spacelab module. The goal of IML-1 was to explore in depth the complex effects of weightlessness of living organisms and materials processing. Around-the-clock research was performed on the human nervous system's adaptation to low gravity and effects of microgravity on other life forms such as shrimp eggs, lentil seedlings, fruit fly eggs, and bacteria. Materials processing experiments were also conducted, including crystal growth from a variety of substances such as enzymes, mercury iodide, and a virus. The Huntsville Operations Support Center (HOSC) Spacelab Payload Operations Control Center (SL POCC) at the Marshall Space Flight Center (MSFC) was the air/ground communication channel used between the astronauts and ground control teams during the Spacelab missions. Featured are activities in the SL POCC during STS-42, IML-1 mission.

  16. Formation of DEG5 and DEG8 complexes and their involvement in the degradation of photodamaged photosystem II reaction center D1 protein in Arabidopsis.

    PubMed

    Sun, Xuwu; Peng, Lianwei; Guo, Jinkui; Chi, Wei; Ma, Jinfang; Lu, Congming; Zhang, Lixin

    2007-04-01

    The widely distributed DEGP proteases play important roles in the degradation of damaged and misfolded proteins. Arabidopsis thaliana contains 16 DEGP-like proteases, four of which are located in the chloroplast. Here, we show that DEG5 and DEG8 form a hexamer in the thylakoid lumen and that recombinant DEG8 is proteolytically active toward both a model substrate (beta-casein) and photodamaged D1 protein of photosystem II (PSII), producing 16-kD N-terminal and 18-kD C-terminal fragments. Inactivation of DEG5 and DEG8 resulted in increased sensitivity to photoinhibition. Turnover of newly synthesized D1 protein in the deg5 deg8 double mutant was impaired, and the degradation of D1 in the presence of the chloroplast protein synthesis inhibitor lincomycin under high-light treatment was slowed in the mutants. Thus, DEG5 and DEG8 are important for efficient turnover of the D1 protein and for protection against photoinhibition in vivo. The deg5 deg8 double mutant showed increased photosensitivity and reduced rates of D1 degradation compared with single mutants of deg5 and deg8. A 16-kD N-terminal degradation fragment of the D1 protein was detected in wild-type plants but not in the deg5 deg8 mutant following in vivo photoinhibition. Therefore, our results suggest that DEG5 and DEG8 have a synergistic function in the primary cleavage of the CD loop of the PSII reaction center protein D1.

  17. C-terminal processing of reaction center protein D1 is essential for the function and assembly of photosystem II in Arabidopsis

    PubMed Central

    Che, Yufen; Fu, Aigen; Hou, Xin; McDonald, Kent; Buchanan, Bob B.; Huang, Weidong; Luan, Sheng

    2013-01-01

    Photosystem II (PSII) reaction center protein D1 is synthesized as a precursor (pD1) with a short C-terminal extension. The pD1 is processed to mature D1 by carboxyl-terminal peptidase A to remove the C-terminal extension and form active protein. Here we report functional characterization of the Arabidopsis gene encoding D1 C-terminal processing enzyme (AtCtpA) in the chloroplast thylakoid lumen. Recombinant AtCtpA converted pD1 to mature D1 and a mutant lacking AtCtpA retained all D1 in precursor form, confirming that AtCtpA is solely responsible for processing. As with cyanobacterial ctpa, a knockout Arabidopsis atctpa mutant was lethal under normal growth conditions but was viable with sucrose under low-light conditions. Viable plants, however, showed deficiencies in PSII and thylakoid stacking. Surprisingly, unlike its cyanobacterial counterpart, the Arabidopsis mutant retained both monomer and dimer forms of the PSII complexes that, although nonfunctional, contained both the core and extrinsic subunits. This mutant was also essentially devoid of PSII supercomplexes, providing an unexpected link between D1 maturation and supercomplex assembly. A knock-down mutant expressing about 2% wild-type level of AtCtpA showed normal growth under low light but was stunted and accumulated pD1 under high light, indicative of delayed C-terminal processing. Although demonstrating the functional significance of C-terminal D1 processing in PSII biogenesis, our study reveals an unsuspected link between D1 maturation and PSII supercomplex assembly in land plants, opening an avenue for exploring the mechanism for the association of light-harvesting complexes with the PSII core complexes. PMID:24043802

  18. Biogenic synthesis of palladium nanoparticles using Pulicaria glutinosa extract and their catalytic activity towards the Suzuki coupling reaction.

    PubMed

    Khan, Mujeeb; Khan, Merajuddin; Kuniyil, Mufsir; Adil, Syed Farooq; Al-Warthan, Abdulrahman; Alkhathlan, Hamad Z; Tremel, Wolfgang; Tahir, Muhammad Nawaz; Siddiqui, Mohammed Rafiq H

    2014-06-28

    Green synthesis of nanomaterials finds the edge over chemical methods due to its environmental compatibility. Herein, we report a facile and eco-friendly method for the synthesis of palladium (Pd) nanoparticles (NPs) using an aqueous solution of Pulicaria glutinosa, a plant widely found in a large region of Saudi Arabia, as a bioreductant. The as-prepared Pd NPs were characterized using ultraviolet-visible (UV-vis) spectroscopy, powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and Fourier transform-infrared spectroscopy (FT-IR). The hydroxyl groups of the plant extract (PE) molecules were found mainly responsible for the reduction and growth of Pd NPs. FT-IR analysis confirmed the dual role of the PE, both as a bioreductant as well as a capping ligand, which stabilizes the surface of Pd NPs. The crystalline nature of the Pd NPs was identified using XRD analysis which confirmed the formation of a face-centered cubic structure (JCPDS: 87-0641, space group: Fm3m (225)). Furthermore, the as-synthesized Pd NPs demonstrated excellent catalytic activity towards the Suzuki coupling reaction under aqueous and aerobic conditions. Kinetic studies of the catalytic reaction monitored using GC confirmed that the reaction completes in less than 5 minutes.

  19. A new approach for the photosynthetic antenna-reaction center complex with a model organized around an s-triazine linker.

    PubMed

    Kuhri, Susanne; Charalambidis, Georgios; Angaridis, Panagiotis A; Lazarides, Theodore; Pagona, Georgia; Tagmatarchis, Nikos; Coutsolelos, Athanassios G; Guldi, Dirk M

    2014-02-10

    Two new artificial mimics of the photosynthetic antenna-reaction center complex have been designed and synthesized (BDP-H2 P-C60 and BDP-ZnP-C60). The resulting electron-donor/acceptor conjugates contain a porphyrin (either in its free-base form (H2P) or as Zn-metalated complex (ZnP)), a boron dipyrrin (BDP), and a fulleropyrrolidine possessing, as substituent of the pyrrolidine nitrogen, an ethylene glycol chain terminating in an amino group C60-X-NH2 (X=spacer). In both cases, the three different components were connected by s-triazine through stepwise substitution reactions of cyanuric chloride. In addition to the facile synthesis, the star-type arrangement of the three photo- and redox-active components around the central s-triazine unit permits direct interaction between one another, in contrast to reported examples in which the three components are arranged in a linear fashion. The energy- and electron-transfer properties of the resulting electron-donor/acceptor conjugates were investigated by using UV/Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. Comparison of the absorption spectra and cyclic voltammograms of BDP-H2P-C60 and BDP-ZnP-C60 with those of BDP-H2P, BDP-ZnP and BDP-C60, which were used as references, showed that the spectroscopic and electrochemical properties of the individual constituents are basically retained, although some appreciable shifts in terms of absorption indicate some interactions in the ground state. Fluorescence lifetime measurements and transient absorption experiments helped to elucidate the antenna function of BDP, which upon selective excitation undergoes a rapid and efficient energy transfer from BDP to H2P or ZnP. This is then followed by an electron transfer to C60, yielding the formation of the singlet charge-separated states, namely BDP-H2(·+) -C60(·-) and BDP-ZnP(·+)-C60(·-). As such, the sequence of energy transfer and electron transfer in the

  20. Insights on activation enthalpy for non-Schmid slip in body-centered cubic metals

    DOE PAGES

    Hale, Lucas M.; Lim, Hojun; Zimmerman, Jonathan A.; ...

    2014-12-18

    We use insights gained from atomistic simulation to develop an activation enthalpy model for dislocation slip in body-centered cubic iron. Furthermore, using a classical potential that predicts dislocation core stabilities consistent with ab initio predictions, we quantify the non-Schmid stress-dependent effects of slip. The kink-pair activation enthalpy is evaluated and a model is identified as a function of the general stress state. Thus, our model enlarges the applicability of the classic Kocks activation enthalpy model to materials with non-Schmid behavior.

  1. X-ray imaging of chemically active valence electrons during a pericyclic reaction

    PubMed Central

    Bredtmann, Timm; Ivanov, Misha; Dixit, Gopal

    2014-01-01

    Time-resolved imaging of chemically active valence electron densities is a long-sought goal, as these electrons dictate the course of chemical reactions. However, X-ray scattering is always dominated by the core and inert valence electrons, making time-resolved X-ray imaging of chemically active valence electron densities extremely challenging. Here we demonstrate an effective and robust method, which emphasizes the information encoded in weakly scattered photons, to image chemically active valence electron densities. The degenerate Cope rearrangement of semibullvalene, a pericyclic reaction, is used as an example to visually illustrate our approach. Our work also provides experimental access to the long-standing problem of synchronous versus asynchronous bond formation and breaking during pericyclic reactions. PMID:25424639

  2. Spatiotemporal regulation of chemical reaction kinetics of cell surface molecules by active remodeling of cortical actin

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, Bhaswati; Chaudhuri, Abhishek; Gowrishankar, Kripa; Mayor, Satyajit; Rao, Madan

    2010-03-01

    Cell surface proteins such as lipid tethered GPI-anchored proteins and Ras-proteins are distributed as monomers and nanoclusters on the surface of living cells. Recent work from our laboratory suggests that the spatial distribution and dynamics of formation and breakup of these nanoclusters is controlled by the active remodeling dynamics of the underlying cortical actin. To explain these observations, we propose a novel mechanism of nanoclustering, involving the transient binding to and advection along constitutively occuring ``asters'' of cortical actin. Here we study the consequences of such active actin based clustering, in the context of chemical reactions involving conformational changes of cell surface proteins. We find that active remodeling of cortical actin, can give rise to a dramatic increase in the reaction efficiency and output levels. In general, such actin driven clustering of membrane proteins could be a cellular mechanism to spatiotemporally regulate and amplify local chemical reaction rates, in the context of signalling and endocytosis.

  3. Synthesis, reactions and biological activity of some new bis-heterocyclic ring compounds containing sulphur atom

    PubMed Central

    2013-01-01

    Background The derivatives of thieno[2,3-b]thiophene belong to a significant category of heterocyclic compounds, which have shown a wide spectrum of medical and industrial application. Results A new building block with two electrophilic center of thieno[2,3-b]thiophene derivatives 2 has been reported by one-pot reaction of diketone derivative 1 with Br2/AcOH in excellent yield. A variety of heteroaromatics having bis(1H-imidazo[1,2a] benzimidazole), bis(1H-imidazo[1,2-b][1,2,4]triazole)-3-methyl-4-phenylthieno[2,3-b]thiophene derivatives, dioxazolo-, dithiazolo-, and 1H-imidazolo-3-methyl-4-phenylthieno[2,3-b]thiophene derivatives as well pyrrolo, thiazolo -3-methyl-4-phenylthieno[2,3-b]thiophene derivatives have been designed, synthesized, characterized, and evaluated for their biological activity. Compounds 3–9 showed good bioassay result. These new derivatives were evaluated for anti-cancer activity against PC-3 cell lines, in vitro antioxidant potential and β-glucuronidase and α-glucosidase inhibitory activities. Compound 3 (IC50 = 56.26 ± 3.18 μM) showed a potent DPPH radical scavenging antioxidant activity and found to be more active than standard N-acetylcystein (IC50 = 105.9 ± 1.1 μM). Compounds 8a (IC50 = 13.2 ± 0.34 μM) and 8b (IC50 = 14.1 ± 0.28 μM) found as potent inhibitor of α-glucusidase several fold more active than the standard acarbose (IC50 = 841 ± 1.73 μM). Most promising results were obtained in β-glucuronidase enzyme inhibition assay. Compounds 5 (IC50 = 0.13 ± 0.019 μM), 6 (IC50 = 19.9 ± 0.285 μM), 8a (IC50 = 1.2 ± 0.0785 μM) and 9 (IC50 = 0.003 ± 0.09 μM) showed a potent inhibition of β-glucuronidase. Compound 9 was found to be several hundred fold more active than standard D-Saccharic acid 1,4-lactone (IC50 = 45.75 ± 2.16 μM). Conclusions Synthesis, characterization, and in vitro biological activity of a series of

  4. [Activities of voivodeship occupational medicine centers in workplace health promotion in 2008].

    PubMed

    Goszczyńska, Eliza

    2010-01-01

    The paper aims to present the activities of the largest Voivodeship Occupational Medicine Centers (VOMCs) in Poland in the area of workplace health promotion in 2008. It was compiled on the basis of written reports concerning these activities sent by the Centers to the Polish National Center for Workplace Health Promotion, Nofer Institute of Occupational Medicine, Łódź. Their analysis shows a greatly varied level of engagement in and understanding of health promotion--from simple single actions (in the field of health education and screening) to long-running programs, including various ways of influencing people the programs are addressed to. In 2008, there were 78 such programs in the country, the most popular of them were those focused on occupational voice disorders and tobacco smoke). VOMCs perceive external factors, unfavorable or indifferent attitudes towards promoting health of their employees on the part of employers as well as financial constraints, as the most common obstacles in undertaking activities in the field of workplace health promotion. At the same time, they link achievements in this field mostly with their own activities, including effective cooperation with various partners and their well qualified and experienced employees.

  5. Optimal waist-to-hip ratios in women activate neural reward centers in men.

    PubMed

    Platek, Steven M; Singh, Devendra

    2010-02-05

    Secondary sexual characteristics convey information about reproductive potential. In the same way that facial symmetry and masculinity, and shoulder-to-hip ratio convey information about reproductive/genetic quality in males, waist-to-hip-ratio (WHR) is a phenotypic cue to fertility, fecundity, neurodevelopmental resources in offspring, and overall health, and is indicative of "good genes" in women. Here, using fMRI, we found that males show activation in brain reward centers in response to naked female bodies when surgically altered to express an optimal (approximately 0.7) WHR with redistributed body fat, but relatively unaffected body mass index (BMI). Relative to presurgical bodies, brain activation to postsurgical bodies was observed in bilateral orbital frontal cortex. While changes in BMI only revealed activation in visual brain substrates, changes in WHR revealed activation in the anterior cingulate cortex, an area associated with reward processing and decision-making. When regressing ratings of attractiveness on brain activation, we observed activation in forebrain substrates, notably the nucleus accumbens, a forebrain nucleus highly involved in reward processes. These findings suggest that an hourglass figure (i.e., an optimal WHR) activates brain centers that drive appetitive sociality/attention toward females that represent the highest-quality reproductive partners. This is the first description of a neural correlate implicating WHR as a putative honest biological signal of female reproductive viability and its effects on men's neurological processing.

  6. Force-activated reactivity switch in a bimolecular chemical reaction at the single molecule level

    NASA Astrophysics Data System (ADS)

    Szoszkiewicz, Robert; Garcia-Manyes, Sergi; Liang, Jian; Kuo, Tzu-Ling; Fernandez, Julio M.

    2009-10-01

    Mechanical force is a distinct and usually less explored way to activate chemical reaction because it can deform the reacting molecules along a well-defined direction of the reaction coordinate. However, the effect of mechanical force on the free- energy surface that governs a chemical reaction is still largely unknown. The combination of protein engineering with single-molecule force-clamp spectroscopy allows us to study the influence of mechanical force on the rate at which a protein disulfide bond is reduced by some reducing agents in a bimolecular substitution reaction (so-called SN2). We found that cleavage of a protein disulfide bond by hydroxide anions exhibits an abrupt reactivity ``switch'' at 500 pN, after which the accelerating effect of force on the rate of an SN2 chemical reaction greatly diminishes. We propose that an abrupt force- induced conformational change of the protein disulfide bond shifts its ground state, drastically changing its reactivity in SN2 chemical reactions. Our experiments directly demonstrate the action of a force-activated switch in the chemical reactivity of a single molecule. References: S. Garcia-Manyes, J. Liang, R. Szoszkiewicz, T-L. Kuo and J. M. Fernandez, Nature Chemistry, 1, 236-242, 2009.

  7. Further insights into the mechanism of the reaction of activated bleomycin with DNA

    PubMed Central

    Chow, Marina S.; Liu, Lei V.; Solomon, Edward I.

    2008-01-01

    Bleomycin (BLM) is a glycopeptide anticancer drug that effectively carries out single- and double-stranded DNA cleavage. Activated BLM (ABLM), a low-spin ferric-hydroperoxide, BLM–FeIII–OOH, is the last intermediate detected before DNA cleavage. We have previously shown through experiments and DFT calculations that both ABLM decay and reaction with H atom donors proceed via direct H atom abstraction. However, the rate of ABLM decay had been previously found, based on indirect methods, to be independent of the presence of DNA. In this study, we use a circular dichroism (CD) feature unique to ABLM to directly monitor the kinetics of ABLM reaction with a DNA oligonucleotide. Our results show that the ABLM + DNA reaction is appreciably faster, has a different kinetic isotope effect, and has a lower Arrhenius activation energy than does ABLM decay. In the ABLM reaction with DNA, the small normal kH/kD ratio is attributed to a secondary solvent effect through DFT vibrational analysis of reactant and transition state (TS) frequencies, and the lower Ea is attributed to the weaker bond involved in the abstraction reaction (C–H for DNA and N–H for the decay in the absence of DNA). The DNA dependence of the ABLM reaction indicates that DNA is involved in the TS for ABLM decay and thus reacts directly with BLM–FeIII–OOH instead of its decay product. PMID:18757754

  8. Assessment of DFT methods for computing activation energies of Mo/W-mediated reactions.

    PubMed

    Hu, Lianrui; Chen, Hui

    2015-10-13

    Using high level ab initio coupled cluster calculations as reference, the performances of 15 commonly used density functionals (DFs) on activation energy calculations for typical Mo/W-mediated reactions have been systematically assessed for the first time in this work. The selected representative Mo/W-mediated reactions cover a wide range from enzymatic reactions to organometallic reactions, which include Mo-catalyzed aldehyde oxidation (aldehyde oxidoreductase), Mo-catalyzed dimethyl sulfoxide (DMSO) reduction (DMSO reductase), W-catalyzed acetylene hydration (acetylene hydratase), Mo/W-mediated olefin metathesis, Mo/W-mediated olefin epoxidation, W-mediated alkyne metathesis, and W-mediated C-H bond activation. Covering both Mo- and W-mediated reactions, four DFs of B2GP-PLYP, M06, B2-PLYP, and B3LYP are uniformly recommended with and without DFT empirical dispersion correction. Among these four DFs, B3LYP is notably improved in performance by DFT empirical dispersion correction. In addition to the absolute value of calculation error, if the trend of DFT results is also a consideration, B2GP-PLYP, B2-PLYP, and M06 keep better performance than other functionals tested and constitute our final recommendation of DFs for both Mo- and W-mediated reactions.

  9. Probing the Energy Transfer Dynamics of Photosynthetic Reaction Center Complexes Through Hole-Burning and Single-Complex Spectroscopy

    SciTech Connect

    Riley, Kerry Joseph

    2007-01-01

    Photosynthesis is the process by which light energy is used to drive reactions that generate sugars to supply energy for cellular processes. It is one of the most important fundamental biological reactions and occurs in both prokaryotic (e.g. bacteria) and eukaryotic (e.g. plants and algae) organisms. Photosynthesis is also remarkably intricate, requiring the coordination of many different steps and reactions in order to successfully transform absorbed solar energy into a biochemical usable form of energy. However, the net reaction for all photosynthetic organisms can be reduced to the following, deceptively general, equation developed by Van Niel[1] H2 - D + Aimplieshv A - H2 + D where H2-D is the electron donor, e.g. H2O, H2S. A is the electron acceptor, e.g. CO2, and A-H2 is the synthesized sugar. Amazingly, this simple net equation is responsible for creating the oxidizing atmosphere of Earth and the recycling of CO2, both of which are necessary for the sustainment of the global ecosystem.

  10. Overview of Iodine Propellant Hall Thruster Development Activities at NASA Glenn Research Center

    NASA Technical Reports Server (NTRS)

    Kamhawi, Hani; Haag, Thomas; Benavides, Gabriel; Hickman, Tyler; Smith, Timothy; Williams, George; Myers, James; Polzin, Kurt; Dankanich, John; Byrne, Larry; Szabo, James; Lee, Lauren

    2016-01-01

    NASA is continuing to invest in advancing Hall thruster technologies for implementation in commercial and government missions. There have been several recent iodine Hall propulsion system development activities performed by the team of the NASA Glenn Research Center, the NASA Marshall Space Flight Center, and Busek Co. Inc. In particular, the work focused on qualification of the 200 W Busek BHT-200-I and the continued development of the 600 W BHT-600-I Hall thruster propulsion systems. This paper presents an overview of these development activities and also reports on the results of short duration tests that were performed on the engineering model BHT-200-I and the development model BHT-600-I Hall thrusters.

  11. In-situ resource utilization activities at the NASA Space Engineering Research Center

    NASA Technical Reports Server (NTRS)

    Ramohalli, Kumar

    1992-01-01

    The paper describes theoretical and experimental research activities at the NASA Space Engineering Research Center aimed at realizing significant cost savings in space missions through the use of locally available resources. The fundamental strategy involves idea generation, scientific screening, feasibility demonstrations, small-scale process plant design, extensive testing, scale-up to realistic production rates, associated controls, and 'packaging', while maintaining sufficient flexibility to respond to national needs in terms of specific applications. Aside from training, the principal activities at the Center include development of a quantitative figure-of-merit to quickly assess the overall mission impact of individual components that constantly change with advancing technologies, extensive tests on a single-cell test bed to produce oxygen from carbon dioxide, and the use of this spent stream to produce methane.

  12. In Situ Imidazole Activation of Ribonucleotides for Abiotic RNA Oligomerization Reactions

    NASA Astrophysics Data System (ADS)

    Burcar, Bradley T.; Jawed, Mohsin; Shah, Hari; McGown, Linda B.

    2015-06-01

    The hypothesis that RNA played a significant role in the origin of life requires effective and efficient abiotic pathways to produce RNA oligomers. The most successful abiotic oligomerization reactions to date have utilized high-energy, modified, or pre-activated ribonucleotides to generate strands of RNA up to 50-mers in length. In spite of their success, these modifications and pre-activation reactions significantly alter the ribonucleotides in ways that are highly unlikely to have occurred on a prebiotic Earth. This research seeks to address this problem by exploring an aqueous based method for activating the canonical ribonucleotides in situ using 1-Ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) and imidazole. The reactions were run with and without a montmorillonite clay catalyst and compared to reactions that used ribonucleotides that were pre-activated with imidazole. The effects of pH and ribonucleotide concentration were also investigated. The results demonstrate the ability of in situ activation of ribonucleotides to generate linear RNA oligomers in solution, providing an alternative route to produce RNA for use in prebiotic Earth scenarios.

  13. The role of surface reactions on the active and selective catalyst design for bioethanol steam reforming

    NASA Astrophysics Data System (ADS)

    Benito, M.; Padilla, R.; Serrano-Lotina, A.; Rodríguez, L.; Brey, J. J.; Daza, L.

    In order to study the role of surface reactions involved in bioethanol steam reforming mechanism, a very active and selective catalyst for hydrogen production was analysed. The highest activity was obtained at 700 °C, temperature at which the catalyst achieved an ethanol conversion of 100% and a selectivity to hydrogen close to 70%. It also exhibited a very high hydrogen production efficiency, higher than 4.5 mol H 2 per mol of EtOH fed. The catalyst was operated at a steam to carbon ratio (S/C) of 4.8, at 700 °C and atmospheric pressure. No by-products, such as ethylene or acetaldehyde were observed. In order to consider a further application in an ethanol processor, a long-term stability test was performed under the conditions previously reported. After 750 h, the catalyst still exhibited a high stability and selectivity to hydrogen production. Based on the intermediate products detected by temperature programmed desorption and reaction (TPD and TPR) experiments, a reaction pathway was proposed. Firstly, the adsorbed ethanol is dehydrogenated to acetaldehyde producing hydrogen. Secondly, the adsorbed acetaldehyde is transformed into acetone via acetic acid formation. Finally, acetone is reformed to produce hydrogen and carbon dioxide, which were the final reaction products. The promotion of such reaction sequence is the key to develop an active, selective and stable catalyst, which is the technical barrier for hydrogen production by ethanol reforming.

  14. Ground reaction forces, kinematics, and muscle activations during the windmill softball pitch.

    PubMed

    Oliver, Gretchen D; Plummer, Hillary

    2011-07-01

    The aims of the present study were to examine quantitatively ground reaction forces, kinematics, and muscle activations during the windmill softball pitch, and to determine relationships between knee valgus and muscle activations, ball velocity and muscle activation as well as ball velocity and ground reaction forces. It was hypothesized that there would be an inverse relationship between degree of knee valgus and muscle activation, a direct relationship between ground reaction forces and ball velocity, and non-stride leg muscle activations and ball velocity. Ten female windmill softball pitchers (age 17.6 ± 3.47 years, stature 1.67 ± 0.07 m, weight 67.4 ± 12.2 kg) participated. Dependent variables were ball velocity, surface electromyographic (sEMG), kinematic, and kinetic data while the participant was the independent variable. Stride foot contact reported peak vertical forces of 179% body weight. There were positive relationships between ball velocity and ground reaction force (r = 0.758, n = 10, P = 0.029) as well as ball velocity and non-stride leg gluteus maximus (r = 0.851, n = 10, P = 0.007) and medius (r = 0.760, n = 10, P = 0.029) muscle activity, while there was no notable relationship between knee valgus and muscle activation. As the windmill softball pitcher increased ball velocity, her vertical ground reaction forces also increased. Proper conditioning of the lumbopelvic-hip complex, including the gluteals, is essential for injury prevention. From the data presented, it is evident that bilateral strength and conditioning of the gluteal muscle group is salient in the windmill softball pitch as an attempt to decrease incidence of injury.

  15. [Activities and responsibilities of workers in embryologic and andrologic laboratories in assisted reproduction centers].

    PubMed

    Záková, J; Trávník, P; Malenovská, A; Hűttelová, R

    2013-11-01

    This paper presents the current status and rules for the laboratory staff activities and their competences in the centers of assisted reproduction. The rules were processed by the members of the Association of Reproductive Embryology (ARE) committee under the current legislation. Committee members of the Czech Sterility and Assisted Reproduction Society and Czech Gynecology and Obstetric Society approved these rules as obligatory for assisted reproduction centres in Czech Republic.

  16. Societal Values and Policies May Curtail Preschool Children’s Physical Activity in Child Care Centers

    PubMed Central

    Sherman, Susan N.; Kendeigh, Cassandra A.; Kalkwarf, Heidi J.; Saelens, Brian E.

    2012-01-01

    BACKGROUND AND OBJECTIVES: Three-fourths of US preschool-age children are in child care centers. Children are primarily sedentary in these settings, and are not meeting recommended levels of physical activity. Our objective was to identify potential barriers to children’s physical activity in child care centers. METHODS: Nine focus groups with 49 child care providers (55% African American) were assembled from 34 centers (inner-city, suburban, Head Start, and Montessori) in Cincinnati, Ohio. Three coders independently analyzed verbatim transcripts for themes. Data analysis and interpretation of findings were verified through triangulation of methods. RESULTS: We identified 3 main barriers to children’s physical activity in child care: (1) injury concerns, (2) financial, and (3) a focus on “academics.” Stricter licensing codes intended to reduce children's injuries on playgrounds rendered playgrounds less physically challenging and interesting. In addition, some parents concerned about potential injury, requested staff to restrict playground participation for their children. Small operating margins of most child care centers limited their ability to install abundant playground equipment. Child care providers felt pressure from state mandates and parents to focus on academics at the expense of gross motor play. Because children spend long hours in care and many lack a safe place to play near their home, these barriers may limit children's only opportunity to engage in physical activity. CONCLUSIONS: Societal priorities for young children—safety and school readiness—may be hindering children’s physical development. In designing environments that optimally promote children’s health and development, child advocates should think holistically about potential unintended consequences of policies. PMID:22218842

  17. Nucleophilic reactions at a vinylic center. XVI. Investigation of the nucleophilic exchange of fluorine in. beta. -fluoroacrylonitriles by the MINDO/3 method

    SciTech Connect

    Shainyan, B.A.

    1986-01-10

    The potential energy surfaces of the reactions of F/sup -/ with cis- and trans-..beta..-fluoroacrylonitriles were calculated by the MINDO/3 method. It was shown that three reaction paths can be realized in the system, i.e., attack by the nucleophile at the ..beta..-carbon atom, the elimination of a proton from the ..cap alpha.. position, and the elimination of a proton from the ..beta.. position. All three reaction paths are exothermic in the gas phase, and the elimination of the proton from the ..cap alpha.. position is 70 kJ/mole more favorable than from the ..beta.. position. Allowance for the effect of the medium in terms of an unconcerted solvation model modes not lead to the appearance of an activation barrier, in contrast to the reactions of anions with ethylene.

  18. Person-Centered, Physical Activity for Patients with Low Back Pain: Piloting Service Delivery

    PubMed Central

    Bloxham, Saul; Barter, Phil; Scragg, Slafka; Peers, Charles; Jane, Ben; Layden, Joe

    2016-01-01

    Low back pain (LBP) is one of the most common and costly conditions in industrialized countries. Exercise therapy has been used to treat LBP, although typically using only one mode of exercise. This paper describes the method and initial findings of a person-centered, group physical activity programme which featured as part of a multidisciplinary approach to treating LBP. Six participants (aged 50.7 ± 17 years) completed a six-week physical activity programme lasting two hours per week. A multicomponent approach to physical activity was adopted which included aerobic fitness, core activation, muscular strength and endurance, Nordic Walking, flexibility and exercise gaming. In addition, participants were required to use diary sheets to record physical activity completed at home. Results revealed significant (p < 0.05) improvements in back strength (23%), aerobic fitness (23%), negative wellbeing (32%) and disability (16%). Person’s Correlation Coefficient analysis revealed significant (p < 0.05) relationships between improvement in perceived pain and aerobic fitness (r = 0.93). It was concluded that a person-centered, multicomponent approach to physical activity may be optimal for supporting patients who self-manage LBP. PMID:27417616

  19. The activity of nanocrystalline Fe-based alloys as electrode materials for the hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Müller, Christian Immanuel; Sellschopp, Kai; Tegel, Marcus; Rauscher, Thomas; Kieback, Bernd; Röntzsch, Lars

    2016-02-01

    In view of alkaline water electrolysis, the activities for the hydrogen evolution reaction of nanocrystalline Fe-based electrode materials were investigated and compared with the activities of polycrystalline Fe and Ni. Electrochemical methods were used to elucidate the overpotential value, the charge transfer resistance and the double layer capacity. Structural properties of the electrode surface were determined with SEM, XRD and XPS analyses. Thus, a correlation between electrochemical and structural parameters was found. In this context, we report on a cyclic voltammetric activation procedure which causes a significant increase of the surface area of Fe-based electrodes leading to a boost in effective activity of the activated electrodes. It was found that the intrinsic activity of activated Fe-based electrodes is very high due to the formation of a nanocrystalline surface layer. In contrast, the activation procedure influences only the intrinsic activity of the Ni electrodes without the formation of a porous surface layer.

  20. Catalytic Activity-d-Band Center Correlation for the O2 Reduction on Platinum in Alkaline Solutions

    SciTech Connect

    Lima,F.; Zhang, J.; Shao, M.; Sasaki, K.; Vukmirovic, M.; Ticianelli, E.; Adzic, R.

    2007-01-01

    We determined, by the rotating disk electrode technique, the kinetics of the oxygen-reduction reaction (ORR) on the surfaces of single crystals of Au(111), Ag(111), Pd(111), Rh(111), Ir(111), and Ru(0001), on Pt monolayers deposited on their surfaces, and also on nanoparticles of these metals dispersed on high-surface-area carbon. Plotting the correlation between the experimentally determined activities of these three types of electrocatalysts with the calculated metal d-band center energies,{var_epsilon}{sub d}, revealed a volcano-type dependence. In all cases, the electronic properties of the metal electrocatalysts, represented by the {var_epsilon}{sub d} value, were used for elucidating the metal-dependent catalytic activities, and establishing their electronic properties-the ORR kinetics relationship. Pt(111), Pt/C, and Pt/Pd(111) were found to top their corresponding volcano plots. Pd in alkaline solutions showed particularly high activity, suggesting it may offer potential replacement for Pt in fuel cells.

  1. The site-directed mutation I(L177)H in Rhodobacter sphaeroides reaction center affects coordination of P(A) and B(B) bacteriochlorophylls.

    PubMed

    Vasilieva, L G; Fufina, T Y; Gabdulkhakov, A G; Leonova, M M; Khatypov, R A; Shuvalov, V A

    2012-08-01

    To explore the influence of the I(L177)H single mutation on the properties of the nearest bacteriochlorophylls (BChls), three reaction centers (RCs) bearing double mutations were constructed in the photosynthetic purple bacterium Rhodobacter sphaeroides, and their properties and pigment content were compared with those of the correspondent single mutant RCs. Each pair of the mutations comprised the amino acid substitution I(L177)H and another mutation altering histidine ligand of BChl P(A) or BChl B(B). Contrary to expectations, the double mutation I(L177)H+H(L173)L does not bring about a heterodimer RC but causes a 46nm blue shift of the long-wavelength P absorbance band. The histidine L177 or a water molecule were suggested as putative ligands for P(A) in the RC I(L177)H+H(L173)L although this would imply a reorientation of the His backbone and additional rearrangements in the primary donor environment or even a repositioning of the BChl dimer. The crystal structure of the mutant I(L177)H reaction center determined to a resolution of 2.9Å shows changes at the interface region between the BChl P(A) and the monomeric BChl B(B). Spectral and pigment analysis provided evidence for β-coordination of the BChl B(B) in the double mutant RC I(L177)H+H(M182)L and for its hexacoordination in the mutant reaction center I(L177)H. Computer modeling suggests involvement of two water molecules in the β-coordination of the BChl B(B). Possible structural consequences of the L177 mutation affecting the coordination of the two BChls P(A) and B(B) are discussed. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: from Natural to Artificial.

  2. Features of the electronic structure of the active center of an HbS molecule

    NASA Astrophysics Data System (ADS)

    Novoselov, D. Yu.; Korotin, Dm. M.; Anisimov, V. I.

    2016-01-01

    Features of the electronic structure of the nonprotein part of the mutant form of the human hemoglobin molecule, HbS, are studied along with the magnetic state of the iron ion that is the "nucleus" of the active center of the molecule. It is found that the mutant form of the HbS molecule differs from a normal hemoglobin molecule by the distortion of the local environment of the iron ion, which changes the energy level splitting by a crystal field. As a result of ab initio calculations, the magnetic transition in the iron atom from the high-spin state to the low-spin state upon the addition of molecular oxygen to hemoglobin molecule is reproduced. It is established for the first time that a change in the crystal and electronic structure of the active center as a result of a mutation can lead to a substantial change in the energy of the bond between the active center of the hemoglobin molecule and an oxygen molecule.

  3. {Delta}G{sup 0} dependence of the electron transfer rate in the photosynthetic reaction center of plant photosystem I: Natural optimization of reaction between chlorophyll a (A{sub 0}) and quinone

    SciTech Connect

    Iwaki, Masayo; Itoh, Shigeru; Kumazaki, Shigeichi; Yoshihara, Keitaro; Erabi, Tatsuo

    1996-06-20

    The rate of the electron transfer reaction from the reduced primary electron acceptor chlorophyll a (A{sub 0}{sup -}) to the secondary acceptor quinone (Q) was measured by picosecond-nanosecond laser spectroscopy at 280 K in the photosynthetic reaction center (RC) complex of plant photosystem I (PS I). The free energy change ({Delta}G{sub 0}) of the reaction was varied between -1.1 and +0.2 eV by the reconstitution of 13 different quinone/quinonoid compounds after the extraction of the intrinsic phylloquinone. Phylloquinone and its natural analog menaquinone, both of which show a {Delta}G{sup 0} value of -0.34 eV, gave the highest rate constant (k) of (23 ps){sup -1}. Analysis of log k versus {Delta}G{sup 0} plot according to the quantum mechanical electron transfer theory gave the total reorganization energy ({lambda}{sub total}) of 0.30 eV and the electronic coupling (V) of 14 cm{sup -1}. The natural system is shown to be highly optimized to give a {Delta}G{sup 0} = -{lambda}{sub total} condition. The {lambda}{sub total} value is smaller and the V value is larger than those estimated in the corresponding reaction between the reduced primary acceptor bacteriopheophytin (H{sup -}) and the secondary acceptor ubiquinone (Q{sub A}) in the purple bacterial RC complex. It is concluded that the A{sub 0}{sup -}Q {yields} A{sub 0}Q{sup -} reaction in the PS I RC occurs in protein environments, which give a low dielectric property, with a shorter electron transfer distance compared to the reaction between H and Q{sub A}. 46 refs., 7 figs., 2 tabs.

  4. Cognate interactions: extrafollicular IL-4 drives germinal-center reactions, a new role for an old cytokine.

    PubMed

    Toellner, Kai-Michael

    2014-07-01

    Over the past 25 years it has become clear that B and T lymphocytes go through a range of interactions and migratory events when B cells differentiate to become high-affinity, antibody-secreting cells. This B-cell differentiation is associated with multiple sequential cognate interactions. In this issue of the European Journal of Immunology, Turqueti-Neves et al. [Eur. J. Immunol. 2014. 44: 2130-2138] show that IL-4, a cytokine well known as a regulator of Ig class switch recombination, has another as-yet-unappreciated role. The authors show that IL-4 produced by T-helper cells outside germinal centers has a major effect on the early stages of germinal-center B-cell differentiation. This Commentary will summarize their findings and relate them to what we know on the sequence of cognate interactions and migratory events B cells undergo during T-dependent immune responses.

  5. Fully converged integral cross sections of collision induced dissociation, four-center, and single exchange reactions, and accuracy of the centrifugal sudden approximation in H2 + D2 reaction.

    PubMed

    Song, Hongwei; Lu, Yunpeng; Lee, Soo-Y

    2012-03-21

    The initial state selected time-dependent wave packet method was employed to calculate the integral cross sections for the H(2) + D(2) reaction with and without the centrifugal sudden (CS) approximation by including all important K (the projection of the total angular momentum on the body-fixed axis) blocks. With a full-dimensional model, the first fully converged coupled-channel (CC) cross sections for different competitive processes from the ground rotational state were obtained: collision induced dissociation (CID), four-center (4C) reaction and single exchange (SE) reaction. The effect of the total angular momentum J on the reaction dynamics of H(2) + D(2) and the accuracy of the CS approximation have also been studied. It was found that the CID and SE processes occur in a wide range of J values while the 4C process can only take place in a narrow window of J values. For this reason, the CC cross section for the 4C channel is merely comparable to the SE channel. A comparison of the integral cross sections from CC and CS calculations showed that the CS approximation works well for the CID process but not for the 4C and SE processes, and the discrepancy between the CC and CS cross sections grows larger as the translational energy and/or the vibrational energy increase(s).

  6. Photocatalytic activity of layered perovskite-like oxides in practically valuable chemical reactions

    NASA Astrophysics Data System (ADS)

    Rodionov, I. A.; Zvereva, I. A.

    2016-03-01

    The photocatalytic properties of layered perovskite-like oxides corresponding to the Ruddlesen-Popper, Dion-Jacobson and Aurivillius phases are considered. Of the photocatalytic reactions, the focus is on the reactions of water splitting, hydrogen evolution from aqueous solutions of organic substances and degradation of model organic pollutants. Possibilities to conduct these reactions under UV and visible light in the presence of layered perovskite-like oxides and composite photocatalysts based on them are shown. The specific surface area, band gap energy, particle morphology, cation and anion doping and surface modification are considered as factors that affect the photocatalytic activity. Special attention is paid to the possibilities to enhance the photocatalytic activity by intercalation, ion exchange and exfoliation, which are inherent in this class of compounds. Conclusions are made about the prospects for the use of layered perovskite-like oxides in photocatalysis. The bibliography includes 253 references.

  7. Cross-section studies of relativistic deuteron reactions on copper by activation method

    NASA Astrophysics Data System (ADS)

    Suchopár, M.; Wagner, V.; Svoboda, O.; Vrzalová, J.; Chudoba, P.; Kugler, A.; Adam, J.; Závorka, L.; Baldin, A.; Furman, W.; Kadykov, M.; Khushvaktov, J.; Solnyshkin, A.; Tsoupko-Sitnikov, V.; Tyutyunnikov, S.

    2015-02-01

    The cross-sections of relativistic deuteron reactions on natural copper were studied in detail by means of activation method. The copper foils were irradiated during experiments with the model spallation targets in the Joint Institute for Nuclear Research. The irradiation of activation samples was performed by beams in the energy range from 1 to 8 GeV. Residual nuclides were measured by the gamma spectrometry. While the EXFOR database contains sets of data for relativistic proton reactions, data for deuteron reactions in this energy range are almost missing. Lack of such experimental cross-section values prevents the use of copper foils from beam integral monitoring. For this reason our experiments focused on their measurement and completely new data were obtained in the energy region where no experimental data have been available so far. The copper monitors with their low sensitivity to fast neutrons will contribute to improvement of the beam integral determination during accelerator-driven system studies.

  8. Chemoselective Boron-Catalyzed Nucleophilic Activation of Carboxylic Acids for Mannich-Type Reactions.

    PubMed

    Morita, Yuya; Yamamoto, Tomohiro; Nagai, Hideoki; Shimizu, Yohei; Kanai, Motomu

    2015-06-10

    The carboxyl group (COOH) is an omnipresent functional group in organic molecules, and its direct catalytic activation represents an attractive synthetic method. Herein, we describe the first example of a direct catalytic nucleophilic activation of carboxylic acids with BH3·SMe2, after which the acids are able to act as carbon nucleophiles, i.e. enolates, in Mannich-type reactions. This reaction proceeds with a mild organic base (DBU) and exhibits high levels of functional group tolerance. The boron catalyst is highly chemoselective toward the COOH group, even in the presence of other carbonyl moieties, such as amides, esters, or ketones. Furthermore, this catalytic method can be extended to highly enantioselective Mannich-type reactions by using a (R)-3,3'-I2-BINOL-substituted boron catalyst.

  9. Communication between Thiamin Cofactors in the Escherichia coli Pyruvate Dehydrogenase Complex E1 Component Active Centers

    PubMed Central

    Nemeria, Natalia S.; Arjunan, Palaniappa; Chandrasekhar, Krishnamoorthy; Mossad, Madouna; Tittmann, Kai; Furey, William; Jordan, Frank

    2010-01-01

    Kinetic, spectroscopic, and structural analysis tested the hypothesis that a chain of residues connecting the 4′-aminopyrimidine N1′ atoms of thiamin diphosphates (ThDPs) in the two active centers of the Escherichia coli pyruvate dehydrogenase complex E1 component provides a signal transduction pathway. Substitution of the three acidic residues (Glu571, Glu235, and Glu237) and Arg606 resulted in impaired binding of the second ThDP, once the first active center was filled, suggesting a pathway for communication between the two ThDPs. 1) Steady-state kinetic and fluorescence quenching studies revealed that upon E571A, E235A, E237A, and R606A substitutions, ThDP binding in the second active center was affected. 2) Analysis of the kinetics of thiazolium C2 hydrogen/deuterium exchange of enzyme-bound ThDP suggests half-of-the-sites reactivity for the E1 component, with fast (activated site) and slow exchanging sites (dormant site). The E235A and E571A variants gave no evidence for the slow exchanging site, indicating that only one of two active sites is filled with ThDP. 3) Titration of the E235A and E237A variants with methyl acetylphosphonate monitored by circular dichroism suggested that only half of the active sites were filled with a covalent predecarboxylation intermediate analog. 4) Crystal structures of E235A and E571A in complex with ThDP revealed the structural basis for the spectroscopic and kinetic observations and showed that either substitution affects cofactor binding, despite the fact that Glu235 makes no direct contact with the cofactor. The role of the conserved Glu571 residue in both catalysis and cofactor orientation is revealed by the combined results for the first time. PMID:20106967

  10. Energetics and excited state dynamics of the radical pair formation in isolated CP47-reaction center complex of photosystem II at various temperatures

    SciTech Connect

    Groot, Marie-Louise; Paa lsson, Lars-Olof; Pribic, Radmila; Stokkum, Ivo H. van; Dekker, Jan P.; Grondelle, Rienk van

    1996-04-01

    The isolated CP47-reaction center complex of spinach photosystem II has been studied with time resolved picosecond fluorescence spectroscopy between 77 K and 270 K. It was observed that these particles exhibit multi-exponential fluorescence decays of the excited state at all temperatures. The major observations are an energy transfer/trapping time of {approx}40 picoseconds and a long-lived {approx}23 nanosecond component attributed to the recombination of the radical pair. These experimentally obtained parameters were used to estimate the free energy difference for the radical pair formation.

  11. The Solar Thermal Design Assistance Center report of its activities and accomplishments in Fiscal Year 1993

    SciTech Connect

    Menicucci, D.F.

    1994-03-01

    The Solar Thermal Design Assistance Center (STDAC) at Sandia National Laboratories is a resource provided by the US Department of Energy`s Solar Thermal Program. Its major objectives are to accelerate the use of solar thermal systems through (a) direct technical assistance to users, (b) cooperative test, evaluation, and development efforts with private industry, and (c) educational outreach activities. This report outlines the major activities and accomplishments of the STDAC in Fiscal Year 1993. The report also contains a comprehensive list of persons who contacted the STDAC by telephone for information or technical consulting.

  12. Reasearch Activities for the Establishment of The Center for Sustainable Energy

    SciTech Connect

    Dr. Michael Seliger

    2005-08-08

    In 2003, Bronx Community College received a grant of $481,000 through the United States Department of Energy for the purpose of conducting research- related activities leading to the creation of the Center for Sustainable Energy at Bronx Community College. The award, which was administered on behalf of Bronx Community College by the Research Foundation of the City University of New York, was initially for one year, from October 2003 through September 30, 2004. It received a no-cost extension to June 30, 2005. This report presents a summary of the activities and accomplishments attributable to the award.

  13. Activities of the Japanese space weather forecast center at Communications Research Laboratory.

    PubMed

    Watari, Shinichi; Tomita, Fumihiko

    2002-12-01

    The International Space Environment Service (ISES) is an international organization for space weather forecasts and belongs to the International Union of Radio Science (URSI). There are eleven ISES forecast centers in the world, and Communications Research Laboratory (CRL) runs the Japanese one. We make forecasts on the space environment and deliver them over the phones and through the Internet. Our forecasts could be useful for human activities in space. Currently solar activity is near maximum phase of the solar cycle 23. We report the several large disturbances of space environment occurred in 2001, during which low-latitude auroras were observed several times in Japan.

  14. Time-resolved FTIR studies provide activation free energy, activation enthalpy and activation entropy for GTPase reactions

    NASA Astrophysics Data System (ADS)

    Kötting, Carsten; Gerwert, Klaus

    2004-12-01

    GTPases, which catalyze the hydrolysis of GTP to GDP and P i, play a key role in the regulation of many biological processes. In this work, we quantify the activation parameters ΔG0∗,ΔH0∗andΔS0∗ for the hydrolysis reaction of GTP in water, in water with Mg 2+ ions and in Ras. Ras belongs to the superfamily of small GTPases (guanine nucleotide-binding proteins; GNBPs). Surprisingly, we find that in all cases, the activation energy consists mainly of enthalpic contributions. Additionally, the small entropic contributions in water and in Ras are similar, so that ΔΔ S* is close to 0. Thus the entropic contributions are only minor in GTPase catalysis and the enthalpic contributions from electrostatic interactions are key to the catalysis. The protein induced change in charge distribution of GTP can be monitored by time-resolved difference FTIR spectroscopy. For Ras the main effect due to protein binding is a charge shift towards the β-phosphate of GTP. This seems to have the main contribution to the catalytic mechanism. Because the G-domain of Ras is highly conserved in GNBPs, we propose that the finding here holds for all GNBPs.

  15. Employing Magnetic Levitation to Monitor Reaction Kinetics and Measure Activation Energy

    ERIC Educational Resources Information Center

    Benz, Lauren; Cesafsky, Karen E.; Le, Tran; Park, Aileen; Malicky, David

    2012-01-01

    This article describes a simple and inexpensive undergraduate-level kinetics experiment that uses magnetic levitation to monitor the progress and determine the activation energy of a condensation reaction on a polymeric solid support. The method employs a cuvette filled with a paramagnetic solution positioned between two strong magnets. The…

  16. Generalization of the Activated Complex Theory of Reaction Rates. II. Classical Mechanical Treatment

    DOE R&D Accomplishments Database

    Marcus, R. A.

    1964-01-01

    In its usual classical form activated complex theory assumes a particular expression for the kinetic energy of the reacting system -- one associated with a rectilinear motion along the reaction coordinate. The derivation of the rate expression given in the present paper is based on the general kinetic energy expression.

  17. Quality-assurance plan for groundwater activities, U.S. Geological Survey, Washington Water Science Center

    USGS Publications Warehouse

    Kozar, Mark D.; Kahle, Sue C.

    2013-01-01

    This report documents the standard procedures, policies, and field methods used by the U.S. Geological Survey’s (USGS) Washington Water Science Center staff for activities related to the collection, processing, analysis, storage, and publication of groundwater data. This groundwater quality-assurance plan changes through time to accommodate new methods and requirements developed by the Washington Water Science Center and the USGS Office of Groundwater. The plan is based largely on requirements and guidelines provided by the USGS Office of Groundwater, or the USGS Water Mission Area. Regular updates to this plan represent an integral part of the quality-assurance process. Because numerous policy memoranda have been issued by the Office of Groundwater since the previous groundwater quality assurance plan was written, this report is a substantial revision of the previous report, supplants it, and contains significant additional policies not covered in the previous report. This updated plan includes information related to the organization and responsibilities of USGS Washington Water Science Center staff, training, safety, project proposal development, project review procedures, data collection activities, data processing activities, report review procedures, and archiving of field data and interpretative information pertaining to groundwater flow models, borehole aquifer tests, and aquifer tests. Important updates from the previous groundwater quality assurance plan include: (1) procedures for documenting and archiving of groundwater flow models; (2) revisions to procedures and policies for the creation of sites in the Groundwater Site Inventory database; (3) adoption of new water-level forms to be used within the USGS Washington Water Science Center; (4) procedures for future creation of borehole geophysics, surface geophysics, and aquifer-test archives; and (5) use of the USGS Multi Optional Network Key Entry System software for entry of routine water-level data

  18. KDD Services at the Goddard Earth Sciences Distributed Active Archive Center

    NASA Technical Reports Server (NTRS)

    Lynnes, Christopher; Mack, Robert; Wharton, Stephen W. (Technical Monitor)

    2000-01-01

    NASA's Goddard Earth Sciences Distributed Active Archive Center (GES DAAC) processes, stores and distributes earth science data from a variety of remote sensing satellites. End users of the data range from instrument scientists to global change and climate researchers to federal agencies and foreign governments. Many of these users apply data mining techniques to large volumes of data (up to 1 TB) received from the GES DAAC. However, rapid advances in processing power are enabling increases in data processing that are outpacing tape drive performance and network capacity. As a result, the proportion of data that can be distributed to users continues to decrease. As mitigation, we are migrating more data mining and mining preparation activities into the data center in order to reduce the data volume that needs to be distributed and to offer the users a more useful and manageable product. This migration of activities faces a number of technical and human-factor challenges. As data reduction and mining algorithms are normally quite specific to the user's research needs, the user's algorithm must be integrated virtually unchanged into the archive environment. Also, the archive itself is busy with everyday data archive and distribution activities and cannot be dedicated to, or even impacted by, the mining activities. Therefore, we schedule KDD 'campaigns' (similar to reprocessing campaigns), during which we schedule a wholesale retrieval of specific data products, offering users the opportunity to extract information from the data being retrieved during the campaign.

  19. Diphenylprolinol silyl ether catalyzed asymmetric Michael reaction of nitroalkanes and β,β-disubstituted α,β-unsaturated aldehydes for the construction of all-carbon quaternary stereogenic centers.

    PubMed

    Hayashi, Yujiro; Kawamoto, Yuya; Honda, Masaki; Okamura, Daichi; Umemiya, Shigenobu; Noguchi, Yuka; Mukaiyama, Takasuke; Sato, Itaru

    2014-09-15

    The asymmetric Michael reaction of nitroalkanes and β,β-disubstituted α,β-unsaturated aldehydes was catalyzed by diphenylprolinol silyl ether to afford 1,4-addition products with an all-carbon quaternary stereogenic center with excellent enantioselectivity. The reaction is general for β-substituents such as β-aryl and β-alkyl groups, and both nitromethane and nitroethane can be employed. The addition of nitroethane is considered a synthetic equivalent of the asymmetric Michael reaction of ethyl and acetyl substituents by means of radical denitration and Nef reaction, respectively. The short asymmetric synthesis of (S)-ethosuximide with a quaternary carbon center was accomplished by using the present asymmetric Michael reaction as the key step. The reaction mechanism that involves the E/Z isomerization of α,β-unsaturated aldehydes, the retro-Michael reaction, and the different reactivity between nitromethane and nitroethane is discussed.

  20. A rapid vectorial back reaction at the reaction centers of photosystem II in tris-washed chloroplasts induced by repetitive flash excitation.

    PubMed

    Renger, G

    1979-07-10

    In Tris-washed chloroplasts, completely lacking the oxygen-evolving capacity, absorption changes in the range of 420--560 nm induced by repetitive flash excitation have been measured in the presence and absence of electron donors. It was found: (1) At 520 nm flash-induced absorption changes are observed, which predominantly decay via a 100--200-mus exponential kinetics corresponding to that of the back reaction between the primary electron donor and acceptor of Photosystem II (Haveman, J. and Mathis, P. (1976) Biochim. Biophys. Acta 440, 346--355; Renger, G. and Wolff, Ch. (1976) Biochim. Biophys. Acta 423, 610--614). In the presence of hydroquinone/ascorbate as donor couple the amplitude is nearly doubled and the decay becomes significantly slowed down. (2) The difference spectrum of the absorption changes obtained in the presence of hydroquinone/ascorbate, which are sensitive to ionophores, is nearly identical with that of normal chloroplasts in the range of 460--560 nm (Emrich, H.M., Junge, W. and Witt, H.T. (1969) Z. Naturforsch. 24b, 114--1146). In the absence of hydroquinone/ascorbate the difference spectrum of the absorption changes, characterized by a 100--200-mus decay kinetics, differs in the range of 460--500 nm and by a hump in the range of 530--560 nm. The hump is shown to be attributable to the socalled C550 absorption change, which reflects the turnover of the primary acceptor of Photosystem II (van Gorkom, H.J.(1976) Thesis, Leiden), while the deviations in the range of 460--500 nm are understandable as to be due to the overlapping absorption changes of chlorphyll alpha II+. The problems arising with the latter explanation are discussed. (3) The electron transfer due to the rapid turnover at Photosystem II, which can be induced by flash groups with a short dark time between the flashes, is not able to energize the ATPase and to drive photophosphorylation. On the basis of the present results it is inferred, that in Tris-washed chloroplasts under

  1. [Standardization of activities in an oncology surgical center according to nursing intervention classification].

    PubMed

    Possari, João Francisco; Gaidzinski, Raquel Rapone; Fugulin, Fernanda Maria Togeiro; Lima, Antônio Fernandes Costa; Kurcgant, Paulina

    2013-06-01

    This study was undertaken in a surgical center specializing in oncology, and it aimed to identify nursing activities performed during the perioperative period and to classify and validate intervention activities according to the Nursing Interventions Classification (NIC). A survey of activities was conducted using records and by direct observation of nursing care across four shifts. Activities were classified as NIC nursing interventions using the cross-mapping technique. The list of interventions was validated by nursing professionals in workshops. Forty-nine interventions were identified: 34 of direct care and 15 of indirect care. Identifying nursing interventions facilitates measuring the time spent in their execution, which is a fundamental variable in the quantification and qualification of nurses' workloads.

  2. Substrate activity of synthetic formyl phosphate in the reaction catalyzed by formyltetrahydrofolate synthetase

    SciTech Connect

    Smithers, G.W.; Jahansouz, H.; Kofron, J.L.; Himes, R.H.; Reed, G.H.

    1987-06-30

    Formyl phosphate, a putative enzyme-bound intermediate in the reaction catalyzed by formyltetrahydrofolate synthetase (EC 6.3.4.3), was synthesized from formyl fluoride and inorganic phosphate, and the product was characterized by /sup 31/P, /sup 1/H, and /sup 13/C nuclear magnetic resonance (NMR). Measurement of hydrolysis rates by /sup 31/P NMR indicates that formyl phosphate is particularly labile, with a half-life of 48 min in a buffered neutral solution at 20 /sup 0/C. At pH 7, hydrolysis occurs with P-O bond cleavage, as demonstrated by /sup 18/O incorporation from H/sub 2//sup 18/O into P/sub i/, while at pH 1 and pH 13 hydrolysis occurs with C-O bond cleavage. The substrate activity of formyl phosphate was tested in the reaction catalyzed by formyltetrahydrofolate synthetase isolated from Clostridium cylindrosporum. Formyl phosphate supports the reaction in both the forward and reverse directions. Thus, N/sup 10/-formyltetrahydrofolate is produced from tetrahydrofolate and formyl phosphate in a reaction mixture that contains enzyme, Mg(II), and ADP, and ATP is produced from formyl phosphate and ADP with enzyme, Mg(II), and tetrahydrofolate present. The requirements for ADP and for tetrahydrofolate as cofactors in these reactions are consistent with previous steady-state kinetic and isotope exchange studies, which demonstrated that all substrate subsites must be occupied prior to catalysis. The k/sub cat/ values for both the forward and reverse directions, with formyl phosphate as the substrate, are much lower than those for the normal forward and reverse reactions. Kinetic analysis of the formyl phosphate supported reactions indicates that the low steady-state rates observed for the synthetic intermediate are most likely due to the sequential nature of the normal reaction.

  3. Vertical flows and structures excited by magnetic activity in the Galactic center region

    NASA Astrophysics Data System (ADS)

    Kakiuchi, Kensuke; Suzuki, Takeru K.; Fukui, Yasuo; Torii, Kazufumi; Machida, Mami; Matsumoto, Ryoji

    2017-01-01

    Various observations show peculiar features in the Galactic Center region, such as loops and filamentary structure. It is still unclear how such characteristic features are formed. Magnetic field is believed to play very important roles in the dynamics of gas in the Galaxy Center. Suzuki et al. (2015) performed a global magneto-hydrodynamical simulation focusing on the Galactic Center with an axisymmetric gravitational potential and claimed that non-radial motion is excited by magnetic activity. We further analyzed their simulation data and found that vertical motion is also excited by magnetic activity. In particular, fast down flows with speed of ~100 km/s are triggered near the footpoint of magnetic loops that are buoyantly risen by Parker instability. These downward flows are accelerated by the vertical component of the gravity, falling along inclined field lines. As a result, the azimuthal and radial components of the velocity are also excited, which are observed as high velocity features in a simulated position-velocity diagram. Depending on the viewing angle, these fast flows will show a huge variety of characteristic features in the position-velocity diagram.

  4. Electro-catalytic activity of Ni–Co-based catalysts for oxygen evolution reaction

    SciTech Connect

    Ju, Hua; Li, Zhihu; Xu, Yanhui

    2015-04-15

    Graphical abstract: The electro-catalytic activity of different electro-catalysts with a porous electrode structure was compared considering the real electrode area that was evaluated by cyclic measurement. - Highlights: • Ni–Co-based electro-catalysts for OER have been studied and compared. • The real electrode area is calculated and used for assessing the electro-catalysts. • Exchange current and reaction rate constant are estimated. • Ni is more useful for OER reaction than Co. - Abstract: In the present work, Ni–Co-based electrocatalysts (Ni/Co = 0:6, 1:5, 2:4, 3:3, 4:2, 5:1 and 6:0) have been studied for oxygen evolution reaction. The phase structure has been analyzed by X-ray diffraction technique. Based on the XRD and SEM results, it is believed that the synthesized products are poorly crystallized. To exclude the disturbance of electrode preparation technology on the evaluation of electro-catalytic activity, the real electrode surface area is calculated based on the cyclic voltammetry data, assumed that the specific surface capacitance is 60 μF cm{sup −2} for metal oxide electrode. The real electrode area data are used to calculate the current density. The reaction rate constant of OER at different electrodes is also estimated based on basic reaction kinetic equations. It is found that the exchange current is 0.05–0.47 mA cm{sup −2} (the real surface area), and the reaction rate constant has an order of magnitude of 10{sup −7}–10{sup −6} cm s{sup −1}. The influence of the electrode potential on OER rate has been also studied by electrochemical impedance spectroscopy (EIS) technique. Our investigation has shown that the nickel element has more contribution than the cobalt; the nickel oxide has the best electro-catalytic activity toward OER.

  5. Overview of Marshall Space Flight Center Activities for the Combustion Stability Tool Development Program

    NASA Technical Reports Server (NTRS)

    Kenny, R. J.; Greene, W. D.

    2016-01-01

    This presentation covers the overall scope, schedule, and activities associated with the NASA - Marshall Space Flight Center (MSFC) involvement with the Combustion Stability Tool Development (CSTD) program. The CSTD program is funded by the Air Force Space & Missile Systems Center; it is approximately two years in duration and; and it is sponsoring MSFC to: design, fabricate, & execute multi-element hardware testing, support Air Force Research Laboratory (AFRL) single element testing, and execute testing of a small-scale, multi-element combustion chamber. Specific MSFC Engineering Directorate involvement, per CSTD-sponsored task, will be outlined. This presentation serves a primer for the corresponding works that provide details of the technical work performed by individual groups within MSFC.

  6. Center for Multiscale Plasma Dynamics: Report on Activities (UCLA/MIT), 2009-2010

    SciTech Connect

    Carter, Troy Alan

    2014-10-03

    The final “phaseout” year of the CMPD ended July 2010; a no cost extension was requested until May 2011 in order to enable the MIT subcontract funds to be fully utilized. Research progress over this time included verification and validation activities for the BOUT and BOUT++ code, studies of spontaneous reconnection in the VTF facility at MIT, and studies of the interaction between Alfv´en waves and drift waves in LAPD. The CMPD also hosted the 6th plasma physics winter school in 2010 (jointly with the NSF frontier center the Center for Magnetic Self-Organization, significant funding came from NSF for this most recent iteration of theWinter School).

  7. Hydrous RuO2 nanoparticles as highly active electrocatalysts for hydrogen evolution reaction

    NASA Astrophysics Data System (ADS)

    Lee, Jooyoung; Sher Shah, Selim Arif; Yoo, Pil J.; Lim, Byungkwon

    2017-04-01

    This letter describes an aqueous-phase synthetic route to hydrous ruthenium oxide (RuO2) nanoparticles and their conversion into crystalline ones via a thermal annealing process. Electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy were employed to characterize hydrous and crystalline RuO2 nanoparticles. The hydrous RuO2 nanoparticles exhibited higher activity for hydrogen evolution reaction than commercial Pt catalyst, while the crystalline RuO2 nanoparticles showed better performance for oxygen evolution reaction than IrO2 catalyst. With these hydrous and crystalline RuO2 catalysts, we were able to achieve highly efficient overall electrochemical water splitting.

  8. Physical activity in child-care centers: do teachers hold the key to the playground?

    PubMed Central

    Copeland, Kristen A.; Kendeigh, Cassandra A.; Saelens, Brian E.; Kalkwarf, Heidi J.; Sherman, Susan N.

    2012-01-01

    Many (56%) US children aged 3–5 years are in center-based childcare and are not obtaining recommended levels of physical activity. In order to determine what child-care teachers/providers perceived as benefits and barriers to children’s physical activity in child-care centers, we conducted nine focus groups and 13 one-on-one interviews with 49 child-care teachers/providers in Cincinnati, OH. Participants noted physical and socio-emotional benefits of physical activity particular to preschoolers (e.g. gross motor skill development, self-confidence after mastery of new skills and improved mood, attention and napping after exercise) but also noted several barriers including their own personal attitudes (e.g. low self-efficacy) and preferences to avoid the outdoors (e.g. don’t like hot/cold weather, getting dirty, chaos of playground). Because individual teachers determine daily schedules and ultimately make the decision whether to take the children outdoors, they serve as gatekeepers to the playground. Participants discussed a spectrum of roles on the playground, from facilitator to chaperone to physical activity inhibitor. These findings suggest that children could have very different gross motor experiences even within the same facility (with presumably the same environment and policies), based on the beliefs, creativity and level of engagement of their teacher. PMID:21804083

  9. Overview of Fluid Dynamics Activities at the Marshall Space Flight Center

    NASA Technical Reports Server (NTRS)

    Garcia, Roberto; Griffin, Lisa W.; Wang, Ten-See

    1999-01-01

    Since its inception 40 years ago, Marshall Space Flight Center (MSFC) has had the need to maintain and advance state-of-the-art flow analysis and cold-flow testing capability to support its roles and missions. This overview discusses the recent organizational changes that have occurred at MSFC with emphasis on the resulting three groups that form the core of fluid dynamics expertise at MSFC: the Fluid Physics and Dynamics Group, the Applied Fluid Dynamics Analysis Group, and the Experimental Fluid Dynamics Group. Recently completed activities discussed include the analysis and flow testing in support of the Fastrac engine design, the X-33 vehicle design, and the X34 propulsion system design. Ongoing activities include support of the RLV vehicle design, Liquid Fly Back Booster aerodynamic configuration definition, and RLV focused technologies development. Other ongoing activities discussed are efforts sponsored by the Center Director's Discretionary Fund (CDDF) to develop an advanced incompressible flow code and to develop optimization techniques. Recently initiated programs and their anticipated required fluid dynamics support are discussed. Based on recent experiences and on the anticipated program needs, required analytical and experimental technique improvements are presented. Due to anticipated budgetary constraints, there is a strong need to leverage activities and to pursue teaming arrangements in order to advance the state-of-the-art and to adequately support concept development. Throughout this overview there is discussion of the lessons learned and of the capabilities demonstrated and established in support of the hardware development programs.

  10. Water-containing hydrogen-bonding network in the active center of channelrhodopsin.

    PubMed

    Ito, Shota; Kato, Hideaki E; Taniguchi, Reiya; Iwata, Tatsuya; Nureki, Osamu; Kandori, Hideki

    2014-03-05

    Channelrhodopsin (ChR) functions as a light-gated ion channel in Chlamydomonas reinhardtii. Passive transport of cations by ChR is fundamentally different from the active transport by light-driven ion pumps such as archaerhodopsin, bacteriorhodopsin, and halorhodopsin. These microbial rhodopsins are important tools for optogenetics, where ChR is used to activate neurons by light, while the ion pumps are used for neural silencing. Ion-transport functions by these rhodopsins strongly depend on the specific hydrogen-bonding networks containing water near the retinal chromophore. In this work, we measured protein-bound water molecules in a chimeric ChR protein of ChR1 (helices A to E) and ChR2 (helices F and G) of Chlamydomonas reinhardtii using low-temperature FTIR spectroscopy at 77 K. We found that the active center of ChR possesses more water molecules (9 water vibrations) than those of other microbial (2-6 water vibrations) and animal (6-8 water vibrations) rhodopsins. We conclude that the protonated retinal Schiff base interacts with the counterion (Glu162) directly, without the intervening water molecule found in proton-pumping microbial rhodopsins. The present FTIR results and the recent X-ray structure of ChR reveal a unique hydrogen-bonding network around the active center of this light-gated ion channel.

  11. Study of the Mn-binding sites in photosystem II using antibodies raised against lumenal regions of the D1 and D2 reaction center proteins

    SciTech Connect

    Dalmasso, E.A.

    1992-04-01

    The experiments discussed in this thesis focus on identifying the protein segments or specific amino acids which provide ligands to the Mn cluster of photosystem II (PS II). This Mn cluster plays a central role in the oxygen-evolving complex (OEC) of PS II. The Mn cluster is thought to be bound by lumenal regions of the PS II reaction center proteins known as D1 and D2. First, several peptides were synthesized which correspond to specific lumenal segments of the D1 and D2 proteins. Next, polyclonal antibodies were successfully elicited using three of these peptides. The peptides recognized by these antibodies correspond to protein segments of the spinach reaction center proteins: Ile-321 to Ala-344 of D1 (D1-a), Asp-319 to Arg-334 of D1 (D1-b), and Val-300 to Asn-319 of D2 (D2-a). These antibodies were then used in assays which were developed to structurally or functionally probe the potential Mn-binding regions of the D1 and D2 proteins.

  12. Protonation of interacting residues in a protein by a Monte Carlo method: application to lysozyme and the photosynthetic reaction center of Rhodobacter sphaeroides.

    PubMed Central

    Beroza, P; Fredkin, D R; Okamura, M Y; Feher, G

    1991-01-01

    We used Monte Carlo methods to treat statistical problem of electrostatic interactions among many titrating amino acids and applied these methods to lysozyme and the photosynthetic reaction center of Rhodobacter sphaeroides, including all titrating sites. We computed the average protonation of residues as a function of pH from an equilibrium distribution of states generated by random sampling. Electrostatic energies were calculated from a finite difference solution to the linearized Poisson-Boltzmann equation using the coordinates from solved protein structures. For most calculations we used the Metropolis algorithm to sample protonation states; for strongly coupled sites, we substantially reduced sampling errors by using a modified algorithm that allows multiple site transitions. The Monte Carlo method agreed with calculations for a small test system, lysozyme, for which the complete partition function was calculated. We also calculated the pH dependence of the free energy change associated with electron transfer from the primary to the secondary quinone in the photosynthetic reaction center. The shape of the resulting curve agreed fairly well with experiment, but the proton uptake from which the free energy was calculated agreed only to within a factor of two with the observed values. We believe that this discrepancy resulted from errors in the individual electrostatic energy calculations rather than from errors in the Monte Carlo sampling. PMID:2062860

  13. Reduction of frontal-plane hip joint reaction force via medio-lateral foot center of pressure manipulation: a pilot study.

    PubMed

    Solomonow-Avnon, Deborah; Wolf, Alon; Herman, Amir; Rozen, Nimrod; Haim, Amir

    2015-02-01

    Footwear-generated biomechanical manipulation of lower-limb joints has been shown to influence lower-limb biomechanics. Numerous studies report the influence of such interventions on the knee, however little is known about the influence of these interventions on the hip. The present study analyzed kinetic and kinematic changes about the hip of 12 healthy young males who underwent biomechanical manipulation utilizing the APOS biomechanical device (APOS-Medical and Sports Technologies Ltd., Herzliya, Israel) allowing controlled foot center of pressure manipulation. Subjects underwent gait testing in four para-sagittal device configurations: Medial, lateral, neutral, and regular shoes. In the medial configuration, subjects demonstrated no change in step width (i.e., distance between right and left foot center of pressure), however inter-malleolar distance significantly increased. Likewise with the medial setting, greater hip abduction was recorded, while hip adduction moment and joint reaction force decreased significantly. We speculate that subjects adopt a modified gait pattern aimed to maintain constant base of support. As a result, hip abductor muscle moment arm increases and adduction moment and joint reaction force decreases. To the best of our knowledge this is the first study to show this relationship. These results contribute to the understanding of lower-limb biomechanics and warrant further investigation.

  14. Tracking Stress and Hydrothermal Activity Along Oceanic Spreading Centers Using Tomographic Images of Seismic Anisotropy

    NASA Astrophysics Data System (ADS)

    Dunn, R. A.; Conder, J. A.; Canales, J. P.

    2014-12-01

    Marine controlled-source seismic tomography experiments now utilize 50+ ocean-bottom seismographs and source grids consisting of many tens of seismic lines with <500 m shot spacing. These dense experiments focus on the upper 10 km of the lithosphere over areas approaching 9000 sq-km. Because of the dense sampling and large azimuthal coverage of ray paths (200,000+ travel time measurements possible), it is now feasible to solve for 3-D images of P-wave azimuthal anisotropy with resolving lengths approaching 1km. Recent examples include the L-SCAN and MARINER experiments, performed at the Eastern Lau Spreading Center and Mid-Atlantic Ridge (36N), respectively. In each case, background anisotropy of ~4% is found in the upper 3-4 km of lithosphere and is consistent with pervasive stress-aligned cracks and microcracks. The fast axes are generally oriented parallel to the trend of the spreading center, as expected for cracks that form in association with seafloor spreading. Three-dimensional images of anisotropy magnitude and orientation reveal variations interpreted as arising from changes in the ambient stress field. Near the ends of ridge segments, where the ridge axis jumps from one spreading center to the next, anisotropy is high with orientations that are out of alignment relative to the background trend. This agrees with numerical models and seafloor morphology that suggest tensile stress concentration and brittle crack formation in these areas. Anisotropy also increases in areas along the ridges where the underlying magma supply and hydrothermal output are greater. This is opposite the trend expected if simple tectonic stress models govern anisotropy. Increased hydrothermal activity, due to increased magma supply, can explain higher anisotropy via increased pore pressure and hydrofracturing. These studies provide the first evidence that images of seismic anisotropy can be used to map variations in hydrologic activity along the crests of oceanic spreading centers.

  15. Time-temperature-transformation curves in chemical reactions regulated by cytoskeletal activity

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Bhaswati; Chaudhuri, Abhishek; Gowrishankar, Kripa; Mayor, Satyajit; Rao, Madan

    2012-02-01

    Efficient and reproducible construction of signaling and sorting complexes, both on the surface and within the living cell, is contingent on local regulation of biochemical reactions by the cellular milieu with active components. We have recently proposed that in many cases this spatiotemporal regulation can be mediated by interaction with components of the dynamic cytoskeleton, where the interplay between active contractility and remodeling of the cytoskeleton results in transient focusing of passive molecules to form clusters, leading to a dramatic increase in the reaction efficiency and output levels. In this presentation, we discuss the implications of actin dynamics by introducing an ``effective temperature,'' which can work as a regulatory parameter for signaling replacing the details of actin dynamics. We show this in time-temperature-transformation plots, with the proposed ``effective temperature'' as a parameter, which paves way for discussion of active chemical thermodynamics.

  16. Effect of detergent concentration on the thermal stability of a membrane protein: The case study of bacterial reaction center solubilized by N,N-dimethyldodecylamine-N-oxide.

    PubMed

    Palazzo, Gerardo; Lopez, Francesco; Mallardi, Antonia

    2010-01-01

    We report on the response of reaction center (RC) from Rhodobacter sphaeroides (an archetype of membrane proteins) to the exposure at high temperature. The RCs have been solubilized in aqueous solution of the detergent N,N-dimethyldodecylamine-N-oxide (LDAO). Changes in the protein conformation have been probed by monitoring the variation in the absorbance of the bacteriochlorine cofactors and modification in the efficiency of energy transfer from tryptophans to cofactors and among the cofactors (through fluorescence measurements). The RC aggregation taking place at high temperature has been investigated by means of dynamic light scattering. Two experimental protocols have been used: (i) isothermal kinetics, in which the time evolution of RC after a sudden increase of the temperature is probed, and (ii) T-scans, in which the RCs are heated at constant rate. The analysis of the results coming from both the experiments indicates that the minimal kinetic scheme requires an equilibrium step and an irreversible process. The irreversible step is characterized by a activation energy of 205+/-14 kJ/mol and is independent from the detergent concentration. Since the temperature dependence of the aggregation rate was found to obey to the same law, the aggregation process is unfolding-limited. On the other hand, the equilibrium process between the native and a partially unfolded conformations was found to be strongly dependent on the detergent concentration. Increasing the LDAO content from 0.025 to 0.5 wt.% decreases the melting temperature from 49 to 42 degrees C. This corresponds to a sizeable (22 kJ/mol at 25 degrees C) destabilization of the native conformation induced by the detergent. The nature of the aggregates formed by the denatured RCs depends on the temperature. For temperature below 60 degrees C compact aggregates are formed while at 60 degrees C the clusters are less dense with a scaling relation between mass and size close to that expected for diffusion

  17. Protonated rhodosemiquinone at the Q(B) binding site of the M265IT mutant reaction center of photosynthetic bacterium Rhodobacter sphaeroides.

    PubMed

    Maróti, Ágnes; Wraight, Colin A; Maróti, Péter

    2015-03-31

    The second electron transfer from primary ubiquinone Q(A) to secondary ubiquinone Q(B) in the reaction center (RC) from Rhodobacter sphaeroides involves a protonated Q(B)(-) intermediate state whose low pK(a) makes direct observation impossible. Here, we replaced the native ubiquinone with low-potential rhodoquinone at the Q(B) binding site of the M265IT mutant RC. Because the in situ midpoint redox potential of Q(A) of this mutant was lowered approximately the same extent (≈100 mV) as that of Q(B) upon exchange of ubiquinone with low-potential rhodoquinone, the inter-quinone (Q(A) → Q(B)) electron transfer became energetically favorable. After subsequent saturating flash excitations, a period of two damped oscillations of the protonated rhodosemiquinone was observed. The Q(B)H(•) was identified by (1) the characteristic band at 420 nm of the absorption spectrum after the second flash and (2) weaker damping of the oscillation at 420 nm (due to the neutral form) than at 460 nm (attributed to the anionic form). The appearance of the neutral semiquinone was restricted to the acidic pH range, indicating a functional pK(a) of <5.5, slightly higher than that of the native ubisemiquinone (pK(a) < 4.5) at pH 7. The analysis of the pH and temperature dependencies of the rates of the second electron transfer supports the concept of the pH-dependent pK(a) of the semiquinone at the Q(B) binding site. The local electrostatic potential is severely modified by the strongly interacting neighboring acidic cluster, and the pK(a) of the semiquinone is in the middle of the pH range of the complex titration. The kinetic and thermodynamic data are discussed according to the proton-activated electron transfer mechanism combined with the pH-dependent functional pK(a) of the semiquinone at the Q(B) site of the RC.

  18. Search for reaction-in-flight neutrons using thulium activation at the National Ignition Facility

    NASA Astrophysics Data System (ADS)

    Grim, Gary; Rundberg, Robert; Tonchev, Anton; Fowler, Malcolm; Wilhelmy, Jerry; Archuleta, Tom; Bionta, Richard; Boswell, Mitzi; Gostic, Julie; Griego, Jeff; Knittel, Kenn; Klein, Andi; Moody, Ken; Shaughnessy, Dawn; Wilde, Carl; Yeamans, Charles

    2013-10-01

    We report on measurements of reaction-in-flight (RIF) neutrons at the National Ignition Facility. RIF neutrons are produced in cryogenically layered implision by up-scattered deuterium, or tritium ions that undergo subsequent fusion reactions. The rate of RIF neutron production is proportional to the fuel areal density (| | R) and ion-stopping length in the dense fuel assembly. Thus, RIF neutrons provide information on charge particle stopping in a strongly coupled plasma, where perturbative modeling breaks down. To measure RIF neutrons, a set of thulium activation foils was placed 50 cm from layered cryogenic implosions at the NIF. The reaction 169Tm(n,3n)167Tm has a neutron kinetic energy threshold of 14.96 MeV. We will present results from initial experiments performed during the spring of 2013. Prepared by LANL under Contract DE-AC-52-06-NA25396, TSPA, LA-UR-13-22085.

  19. Activation cross sections for reactions induced by 14 MeV neutrons on natural tantalum

    SciTech Connect

    Luo Junhua; Tuo Fei; Kong Xiangzhong

    2009-05-15

    Cross sections for (n,2n), (n,p), (n,n{sup '}{alpha}), (n,t), (n,d{sup '}), and (n,{alpha}) reactions have been measured on tantalum isotopes at the neutron energies of 13.5 to 14.7 MeV using the activation technique. Data are reported for the following reactions: {sup 181}Ta(n,2n){sup 180}Ta{sup g}, {sup 181}Ta(n,p){sup 181}Hf, {sup 181}Ta(n,n{sup '}{alpha}){sup 177}Lu{sup m}, {sup 181}Ta(n,t){sup 179}Hf{sup m2}, {sup 181}Ta(n,d{sup '}){sup 180}Hf{sup m}, and {sup 181}Ta(n,{alpha}){sup 178}Lu{sup m}. The neutron fluences were determined using the monitor reaction {sup 27}Al(n,{alpha}){sup 24}Na. Results were discussed and compared with the previous works.

  20. Activation and implementation of a Federal Radiological Monitoring and Assessment Center

    SciTech Connect

    Doyle, J.F. III

    1989-01-01

    The Nevada Operations Office of the U.S. Department of Energy (DOE/NV) has been assigned the primary responsibility for responding to a major radiological emergency. The initial response to any radiological emergency, however, will probably be conducted under the DOE regional radiological assistance plan (RAP). If the dimensions of the crisis demand federal assistance, the following sequence of events may be anticipated: (1) DOE regional RAP response, (2) activation of the Federal Radiological Monitoring and Assistance Center (FRMAC) requested, (3) aerial measuring systems and DOE/NV advance party respond, (4) FRMAC activated, (5) FRMAC responds to state(s) and cognizant federal agency (CFA), and (6) management of FRMAC transferred to the Environmental Protection Agency (EPA). The paper discusses activation channels, authorization, notification, deployment, and interfaces.

  1. Results From the Bipartisan Policy Center's CEO Council Physical Activity Challenge to American Business

    PubMed Central

    Berko, Jeff; Goetzel, Ron Z.; Roemer, Enid Chung; Kent, Karen; Marchibroda, Janet

    2016-01-01

    Objective: The aim of this study was to describe findings from a survey of employees at 10 businesses participating in the “Building Better Health: Physical Activity Challenge,” an effort led by the Bipartisan Policy Center's CEO Council on Health and Innovation. Methods: Employers provided employees with pedometers as part of an 8-week Physical Activity Challenge (Challenge). Employees were then asked to complete a survey about their awareness of, participation in, and satisfaction with the Challenge. Results: One hundred three thousand three hundred eighty-three employees participated in the Challenge, averaging 6886 steps per day per participant. Of the 3820 respondents to an employee survey sent to all workers, 62% reported enrolling in the program, and of those, the majority reported positive impacts on health (76%), fitness (73%), and lifestyle (70%). Conclusion: A brief, workplace-based physical activity challenge can achieve positive self-reported health impacts when supported by senior management of the company. PMID:27930485

  2. Active specific immunotherapy using the immune reaction of a low-dose irradiated tumor tissue. [Mice

    SciTech Connect

    Ogawa, Y.; Imanaka, K.; Ashida, C.; Takashima, H.; Imajo, Y.; Kimura, S.

    1983-04-01

    Active specific immunotherapy using the immune reaction of a low-dose irradiated tumor tissue was studied on the transplanted MM46 tumor of female C3H/He mice after radiotherapy. MM46 tumor cells were inoculated into the right hind paws of mice. On the 5th day, irradiation with the dose irradiated tumor tissue (2000 rad on the fifth day), were injected into the left hind paws of the tumor-bearing mice. Effectiveness of this active specific immunotherapy against tumor was evaluated by the regression of tumor and survival rate of mice. Tumor was markedly regressed and survival rate was significantly increased by the active specific immunitherapy.

  3. Structure and catalytic activities of ferrous centers confined on the interface between carbon nanotubes and humic acid

    NASA Astrophysics Data System (ADS)

    Wang, Bing; Zhou, Xiaoyan; Wang, Dongqi; Yin, Jun-Jie; Chen, Hanqing; Gao, Xingfa; Zhang, Jing; Ibrahim, Kurash; Chai, Zhifang; Feng, Weiyue; Zhao, Yuliang

    2015-01-01

    ferrous sites. The experimental and theoretical results revealed octahedrally/tetrahedrally coordinated geometry at Fe centers, and the strong hybridization between CNT C π* and Fe 3d orbitals induces discretization of the atomic charges on aromatic rings of CNTs, which facilitates O2 adsorption and electron transfer from carbon to O2, which enhances O2 activation. The O2 activation by the novel HA/Fe-CNT complex can be applied in the oxidative degradation of phenol red (PR) and bisphenol A (BPA) in aqueous media. Electronic supplementary information (ESI) available: Optimization of the mass ratios of HA to CNTs and the reaction pH conditions for Fe loading; scanning electron microscope (SEM), UV-Vis-near-infrared, Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) for CNT-HA; EPR experiment and UPLC-ESI-MS analysis; and DFT calculation. See DOI: 10.1039/c4nr06665k

  4. Results of the pilot proof of the inquiry activities conducted in the science center

    NASA Astrophysics Data System (ADS)

    Kireš, Marián; BilišÅanská, Mária

    2017-01-01

    The science center SteelPARK Košice offers more than 60 interactive exhibits focused on presenting scientific principles and technical solutions connected to the production and manufacture of steel, research of its properties and its various industrial uses. We are trying to enhance the attractivity of the modern style of the exhibitions and its potential to engage students of ground and middle schools in acquiring new knowledge and capabilities, by means of the inquiry science center. Two laboratory measurements, for 5 three-person teams are provided once a month. During the introductory discussion on the activity, they are asked to answer a series of conceptual questions, which help determine their level of understanding at the beginning of the exercise. The measurements are based in guided inquiry, where the work progress is given a forehand, but the desired result is not. Every activity is focused on developing specific research capabilities. This is being monitored through a self-evaluation card, which every participants is required to fill out immediately after completing the activity. The work is tutored by a lecturer from the students of didactics. During two years and running 15 different activities, we have been able to gather information from more than 6000 students of ground and middle schools. Specific physics measurements, their respective conceptual questions, worksheets and final reports are being presented in this article. We evaluate the present level of conceptual understanding based on the acquired data and give recommendation to teachers on ways to improve the student's capabilities. The teacher, by way of observing the activity, the work of the lecturer and the students, is able to form an understanding of the inquiry activity for their own school practice, for which he/she can use all available methodical and work materials.

  5. Daily activity and light exposure levels for five species of lemurs at the Duke Lemur Center.

    PubMed

    Rea, Mark S; Figueiro, Mariana G; Jones, Geoffrey E; Glander, Kenneth E

    2014-01-01

    Light is the primary synchronizer of all biological rhythms, yet little is known about the role of the 24-hour luminous environment on nonhuman primate circadian patterns, making it difficult to understand the photic niche of the ancestral primate. Here we present the first data on proximate light-dark exposure and activity-rest patterns in free-ranging nonhuman primates. Four individuals each of five species of lemurs at the Duke Lemur Center (Eulemur mongoz, Lemur catta, Propithecus coquereli, Varecia rubra, and Varecia variegata variegata) were fitted with a Daysimeter-D pendant that contained light and accelerometer sensors. Our results reveal common as well as species-specific light exposure and behavior patterns. As expected, all five species were more active between sunrise and sunset. All five species demonstrated an anticipatory increase in their pre-sunrise activity that peaked at sunrise with all but V. rubra showing a reduction within an hour. All five species reduced activity during mid-day. Four of the five stayed active after sunset, but P. coquereli began reducing their activity about 2 hours before sunset. Other subtle differences in the recorded light exposure and activity patterns suggest species-specific photic niches and behaviors. The eventual application of the Daysimeter-D in the wild may help to better understand the adaptive evolution of ancestral primates.

  6. Suppression of oxygen reduction reaction activity on Pt-based electrocatalysts from ionomer incorporation

    SciTech Connect

    Shinozaki, Kazuma; Morimoto, Yu; Pivovar, Bryan S.; Kocha, Shyam S.

    2016-09-01

    The impact of Nafion on the oxygen reduction reaction (ORR) activity is studied for Pt/C and Pt-alloy/C catalysts using thin-film rotating disk electrode (TF-RDE) methods in 0.1 M HClO4. Ultrathin uniform catalyst layers and standardized activity measurement protocols are employed to obtain accurate and reproducible ORR activity. Nafion lowers the ORR activity which plateaus with increasing loading on Pt catalysts. Pt particle size is found not to have significant influence on the extent of the SA decrease upon Nafion incorporation. Catalysts using high surface area carbon (HSC) support exhibit attenuated activity loss resulting from lower ionomer coverage on catalyst particles located within the deep pores. The impact of metallic composition on the activity loss due to Nafion incorporation is also discussed.

  7. The Biginelli reaction with an imidazolium-tagged recyclable iron catalyst: kinetics, mechanism, and antitumoral activity.

    PubMed

    Ramos, Luciana M; Guido, Bruna C; Nobrega, Catharine C; Corrêa, José R; Silva, Rafael G; de Oliveira, Heibbe C B; Gomes, Alexandre F; Gozzo, Fábio C; Neto, Brenno A D

    2013-03-25

    The present work describes the synthesis, characterization, and application of a new ion-tagged iron catalyst. The catalyst was employed in the Biginelli reaction with impressive performance. High yields have been achieved when the reaction was carried out in imidazolium-based ionic liquids (BMI⋅PF6, BMI⋅NTf2, and BMI⋅BF4), thus showing that the ionic-liquid effects play a role in the reaction. Moreover, the ion-tagged catalyst could be recovered and reused up to eight times without any noticeable loss in activity. Mechanistic studies performed by using high-resolution electrospray-ionization quadrupole-time-of-flight mass (HR-EI-QTOF) spectrometry and kinetic experiments indicate only one reaction pathway and rule out the other two possibilities under the development conditions. The theoretical calculations are in accordance with the proposed mechanism of action of the iron catalyst. Finally, the 37 dihydropyrimidinone derivatives, products of the Biginelli reaction, had their cytotoxicity evaluated in assays against MCF-7 cancer cell linages with encouraging results of some derivatives, which were virtually non-toxic against healthy cell linages (fibroblasts).

  8. Force-activated reactivity switch in a bimolecular chemical reaction at the single molecule level

    NASA Astrophysics Data System (ADS)

    Szoszkiewicz, Robert; Garcia-Manyes, Sergi; Liang, Jian; Kuo, Tzu-Ling; Fernandez, Julio M.

    2010-03-01

    Mechanical force can deform the reacting molecules along a well-defined direction of the reaction coordinate. However, the effect of mechanical force on the free-energy surface that governs a chemical reaction is still largely unknown. The combination of protein engineering with single-molecule AFM force-clamp spectroscopy allows us to study the influence of mechanical force on the rate at which a protein disulfide bond is reduced by some reducing agents in a bimolecular substitution reaction (so-called SN2). We found that cleavage of a protein disulfide bond by hydroxide anions exhibits an abrupt reactivity ``switch'' at 500 pN, after which the accelerating effect of force on the rate of an SN2 chemical reaction greatly diminishes. We propose that an abrupt force-induced conformational change of the protein disulfide bond shifts its ground state, drastically changing its reactivity in SN2 chemical reactions. Our experiments directly demonstrate the action of a force-activated switch in the chemical reactivity of a single molecule. References: Sergi Garcia-Manyes, Jian Liang, Robert Szoszkiewicz, Tzu-Ling Kuo and Julio M. Fernandez, Nature Chemistry, 1, 236-242, 2009.

  9. Cold-induced precipitation of a monoclonal IgM: a negative activation enthalpy reaction.

    PubMed

    Meliga, Stefano C; Farrugia, William; Ramsland, Paul A; Falconer, Robert J

    2013-01-17

    Cold-induced precipitation of a monoclonal IgM cryoglobulin isolated from a patient with Waldenström's macroglobulinemia was observed to have a negative activation enthalpy. The rate of the reaction increased, as the temperature decreased. Differential scanning calorimetry of the monoclonal IgM showed precipitation as an inverted peak during a downward temperature scan. The transition temperature was between 14 and 15 °C and was possibly concentration dependent. At temperatures below the transition the precipitation was best described by second-order kinetics. The difference in change in enthalpy between precipitation and disassociation suggests that cold-induced precipitation had a fast precipitation stage followed by a slower consolidation reaction. Negligible curvature of the Eyring plot suggested the precipitation reaction was dominated by van der Waal forces and hydrogen bonding. Conversely, during an upward temperature scan, disassociation was observed as a positive enthalpy peak. This reaction had two stages, a reaction undoing consolidation followed by heat-induced disassociation that had first-order kinetics.

  10. Clinical process analysis and activity-based costing at a heart center.

    PubMed

    Ridderstolpe, Lisa; Johansson, Andreas; Skau, Tommy; Rutberg, Hans; Ahlfeldt, Hans

    2002-08-01

    Cost studies, productivity, efficiency, and quality of care measures, the links between resources and patient outcomes, are fundamental issues for hospital management today. This paper describes the implementation of a model for process analysis and activity-based costing (ABC)/management at a Heart Center in Sweden as a tool for administrative cost information, strategic decision-making, quality improvement, and cost reduction. A commercial software package (QPR) containing two interrelated parts, "ProcessGuide and CostControl," was used. All processes at the Heart Center were mapped and graphically outlined. Processes and activities such as health care procedures, research, and education were identified together with their causal relationship to costs and products/services. The construction of the ABC model in CostControl was time-consuming. However, after the ABC/management system was created, it opened the way for new possibilities including process and activity analysis, simulation, and price calculations. Cost analysis showed large variations in the cost obtained for individual patients undergoing coronary artery bypass grafting (CABG) surgery. We conclude that a process-based costing system is applicable and has the potential to be useful in hospital management.

  11. Galactic Center gamma-ray ``excess'' from an active past of the Galactic Centre?

    NASA Astrophysics Data System (ADS)

    Petrović, Jovana; Dario Serpico, Pasquale; Zaharijaš, Gabrijela

    2014-10-01

    Several groups have recently claimed evidence for an unaccounted gamma-ray excess over the diffuse backgrounds at few GeV in the Fermi-LAT data in a region around the Galactic Center, consistent with a dark matter annihilation origin. We demonstrate that the main spectral and angular features of this excess can be reproduced if they are mostly due to inverse Compton emission from high-energy electrons injected in a burst event of ~ 1052÷1053 erg roughly Script O(106) years ago. We consider this example as a proof of principle that time-dependent phenomena need to be understood and accounted for—together with detailed diffuse foregrounds and unaccounted ``steady state'' astrophysical sources—before any robust inference can be made about dark matter signals at the Galactic Center. In addition, we point out that the timescale suggested by our study, which controls both the energy cutoff and the angular extension of the signal, intriguingly matches (together with the energy budget) what is indirectly inferred by other evidences suggesting a very active Galactic Center in the past, for instance related to intense star formation and accretion phenomena.

  12. Activities in the Payload Operation Control Center at MSFC During the IML-1 Mission

    NASA Technical Reports Server (NTRS)

    1992-01-01

    This photograph shows activities during the International Microgravity Laboratory-1 (IML-1) mission (STS-42) in the Payload Operations Control Center (POCC) at the Marshall Space Flight Center. The IML-1 mission was the first in a series of Shuttle flights dedicated to fundamental materials and life sciences research. The mission was to explore, in depth, the complex effects of weightlessness on living organisms and materials processing. The crew conducted experiments on the human nervous system's adaptation to low gravity and the effects on other life forms such as shrimp eggs, lentil seedlings, fruit fly eggs, and bacteria. Low gravity materials processing experiments included crystal growth from a variety of substances such as enzymes, mercury, iodine, and virus. The International space science research organizations that participated in this mission were: The U.S. National Aeronautics and Space Administration, the European Space Agency, the Canadian Space Agency, the French National Center for Space Studies, the German Space Agency, and the National Space Development Agency of Japan. The POCC was the air/ground communication charnel used between the astronauts aboard the Spacelab and scientists, researchers, and ground control teams during the Spacelab missions. The facility made instantaneous video and audio communications possible for scientists on the ground to follow the progress and to send direct commands of their research almost as if they were in space with the crew.

  13. Joint Spacelab-J (SL-J) Activities at the Huntsville Operations Support Center (HOSC) Spacelab

    NASA Technical Reports Server (NTRS)

    1999-01-01

    The science laboratory, Spacelab-J (SL-J), flown aboard the STS-47 flight was a joint venture between NASA and the National Space Development Agency of Japan (NASDA) utilizing a manned Spacelab module. The mission conducted 24 materials science and 20 life science experiments, of which 35 were sponsored by NASDA, 7 by NASA, and two collaborative efforts. Materials science investigations covered such fields as biotechnology, electronic materials, fluid dynamics and transport phenomena, glasses and ceramics, metals and alloys, and acceleration measurements. Life sciences included experiments on human health, cell separation and biology, developmental biology, animal and human physiology and behavior, space radiation, and biological rhythms. Test subjects included the crew, Japanese koi fish (carp), cultured animal and plant cells, chicken embryos, fruit flies, fungi and plant seeds, and frogs and frog eggs. Featured together in joint ground activities during the SL-J mission are NASA/NASDA personnel at the Huntsville Operations Support Center (HOSC) Spacelab Payload Operations Control Center (SL POCC) at Marshall Space Flight Center (MSFC).

  14. Activities in the Payload Operations Control Center at MSFC During the IML-1 Mission

    NASA Technical Reports Server (NTRS)

    1992-01-01

    This photograph shows activities during the International Microgravity Laboratory-1 (IML-1) mission (STS-42) in the Payload Operations Control Center (POCC) at the Marshall Space Flight Center. Members of the Fluid Experiment System (FES) group monitor the progress of their experiment through video at the POCC. The IML-1 mission was the first in a series of Shuttle flights dedicated to fundamental materials and life sciences research. The mission was to explore, in depth, the complex effects of weightlessness on living organisms and materials processing. The crew conducted experiments on the human nervous system's adaptation to low gravity and the effects on other life forms such as shrimp eggs, lentil seedlings, fruit fly eggs, and bacteria. Low gravity materials processing experiments included crystal growth from a variety of substances such as enzymes, mercury, iodine, and virus. The International space science research organizations that participated in this mission were: The U.S. National Aeronautics and Space Administion, the European Space Agency, the Canadian Space Agency, the French National Center for Space Studies, the German Space Agency, and the National Space Development Agency of Japan. The POCC was the air/ground communication charnel used between astronauts aboard the Spacelab and scientists, researchers, and ground control teams during the Spacelab missions. The facility made instantaneous video and audio communications possible for scientists on the ground to follow the progress and to send direct commands of their research almost as if they were in space with the crew.

  15. Galactic Center gamma-ray ''excess'' from an active past of the Galactic Centre?

    SciTech Connect

    Petrović, Jovana; Serpico, Pasquale Dario; Zaharijaš, Gabrijela E-mail: serpico@lapth.cnrs.fr

    2014-10-01

    Several groups have recently claimed evidence for an unaccounted gamma-ray excess over the diffuse backgrounds at few GeV in the Fermi-LAT data in a region around the Galactic Center, consistent with a dark matter annihilation origin. We demonstrate that the main spectral and angular features of this excess can be reproduced if they are mostly due to inverse Compton emission from high-energy electrons injected in a burst event of ∼ 10{sup 52}÷10{sup 53} erg roughly O(10{sup 6}) years ago. We consider this example as a proof of principle that time-dependent phenomena need to be understood and accounted for—together with detailed diffuse foregrounds and unaccounted ''steady state'' astrophysical sources—before any robust inference can be made about dark matter signals at the Galactic Center. In addition, we point out that the timescale suggested by our study, which controls both the energy cutoff and the angular extension of the signal, intriguingly matches (together with the energy budget) what is indirectly inferred by other evidences suggesting a very active Galactic Center in the past, for instance related to intense star formation and accretion phenomena.

  16. Spin state transition in the active center of the hemoglobin molecule: DFT + DMFT study

    NASA Astrophysics Data System (ADS)

    Novoselov, D.; Korotin, Dm. M.; Anisimov, V. I.

    2016-05-01

    An ab initio study of electronic and spin configurations of the iron ion in the active center of the human hemoglobin molecule is presented. With a combination of the Density Functional Theory (DFT) method and the Dynamical Mean Field Theory (DMFT) approach, the spin state transition description in the iron ion during the oxidation process is significantly improved in comparison with previous attempts. It was found that the origin of the iron ion local moment behavior both for the high-spin and for the low-spin states in the hemoglobin molecule is caused by the presence of a mixture of several atomic states with comparable statistical probability.

  17. JPL Physical Oceanography Distributed Active Archive Center (PO.DAAC) data availability, version 1-94

    NASA Technical Reports Server (NTRS)

    1994-01-01

    The Physical Oceanography Distributed Active Archive Center (PO.DAAC) archive at the Jet Propulsion Laboratory (JPL) includes satellite data sets for the ocean sciences and global-change research to facilitate multidisciplinary use of satellite ocean data. Parameters include sea-surface height, surface-wind vector, sea-surface temperature, atmospheric liquid water, and integrated water vapor. The JPL PO.DAAC is an element of the Earth Observing System Data and Information System (EOSDIS) and is the United States distribution site for Ocean Topography Experiment (TOPEX)/POSEIDON data and metadata.

  18. Wind tunnel productivity status and improvement activities at NASA Langley Research Center

    NASA Technical Reports Server (NTRS)

    Putnam, Lawrence E.

    1996-01-01

    Over the last three years, a major effort has been underway to re-engineering the way wind tunnel testing is accomplished at the NASA Langley Research Center. This effort began with the reorganization of the LaRC and the consolidation of the management of the wind tunnels in the Aerodynamics Division under one operations branch. This paper provides an overview of the re-engineering activities and gives the status of the improvements in the wind tunnel productivity and customer satisfaction that have resulted from the new ways of working.

  19. Contents of the JPL Distributed Active Archive Center (DAAC) archive, version 2-91

    NASA Technical Reports Server (NTRS)

    Smith, Elizabeth A. (Editor); Lassanyi, Ruby A. (Editor)

    1991-01-01

    The Distributed Active Archive Center (DAAC) archive at the Jet Propulsion Laboratory (JPL) includes satellite data sets for the ocean sciences and global change research to facilitate multidisciplinary use of satellite ocean data. Parameters include sea surface height, surface wind vector, sea surface temperature, atmospheric liquid water, and surface pigment concentration. The Jet Propulsion Laboratory DAAC is an element of the Earth Observing System Data and Information System (EOSDIS) and will be the United States distribution site for the Ocean Topography Experiment (TOPEX)/POSEIDON data and metadata.

  20. Some Investigations of the Reaction of Activated Charcoal with Fluorine and Uranium Hexafluoride

    SciTech Connect

    Del Cul, G.D.; Fiedor, J.N.; Simmons, D.W.; Toth, L.M.; Trowbridge, L.D.; Williams

    1998-09-01

    The Molten Salt Reactor Experiment (MSRE) at Oak Ridge National Laboratory has been shut down since 1969, when the fuel salt was drained from the core into two Hastelloy N drain tanks at the reactor site. Over time, fluorine (F{sub 2}) and uranium hexafluoride (UF{sub 6}) moved from the salt through the gas piping to a charcoal bed, where they reacted with the activated charcoal. Some of the immediate concerns related to the migration of F{sub 2} and UF{sub 6} to the charcoal bed were the possibility of explosive reactions between the charcoal and F{sub 2}, the existence of conditions that could induce a criticality accident, and the removal and recovery of the fissile uranium from the charcoal. This report addresses the reactions and reactivity of species produced by the reaction of fluorine and activated charcoal and between charcoal and F{sub 2}-UF{sub 6} gas mixtures in order to support remediation of the MSRE auxiliary charcoal bed (ACB) and the recovery of the fissile uranium. The chemical identity, stoichiometry, thermochemistry, and potential for explosive decomposition of the primary reaction product, fluorinated charcoal, was determined.

  1. Dioxygen activation by non-adiabatic oxidative addition to a single metal center [O2 activation by non-adiabatic oxidative addition to a single metal center

    SciTech Connect

    Akturk, Eser S.; Yap, Glenn P. A.; Theopold, Klaus H.

    2015-10-16

    A chromium(I) dinitrogen complex reacts rapidly with O2 to form the mononuclear dioxo complex [TptBu,MeCrV(O)2] (TptBu,Me=hydrotris(3-tert-butyl-5-methylpyrazolyl)borate), whereas the analogous reaction with sulfur stops at the persulfido complex [TptBu,MeCrIII(S2)]. The transformation of the putative peroxo intermediate [TptBu,MeCrIII(O2)] (S=3/2) into [TptBu,MeCrV(O)2] (S=1/2) is spin-forbidden. The minimum-energy crossing point for the two potential energy surfaces has been identified. Finally, although the dinuclear complex [(TptBu,MeCr)2(μ-O)2] exists, mechanistic experiments suggest that O2 activation occurs on a single metal center, by an oxidative addition on the quartet surface followed by crossover to the doublet surface.

  2. 75 FR 7474 - CenterPoint Energy Gas Transmission Company; Prior Notice of Activity Under Blanket Certificate

    Federal Register 2010, 2011, 2012, 2013, 2014

    2010-02-19

    ... Energy Regulatory Commission CenterPoint Energy Gas Transmission Company; Prior Notice of Activity Under Blanket Certificate February 3, 2010. On January 26, 2010 CenterPoint Energy Gas Transmission Company... Energy Regulatory Commission's (Commission) regulations under the Natural Gas Act, and CEGT's...

  3. Biophysical assay for tethered signaling reactions reveals tether-controlled activity for the phosphatase SHP-1.

    PubMed

    Goyette, Jesse; Salas, Citlali Solis; Coker-Gordon, Nicola; Bridge, Marcus; Isaacson, Samuel A; Allard, Jun; Dushek, Omer

    2017-03-01

    Tethered enzymatic reactions are ubiquitous in signaling networks but are poorly understood. A previously unreported mathematical analysis is established for tethered signaling reactions in surface plasmon resonance (SPR). Applying the method to the phosphatase SHP-1 interacting with a phosphorylated tether corresponding to an immune receptor cytoplasmic tail provides five biophysical/biochemical constants from a single SPR experiment: two binding rates, two catalytic rates, and a reach parameter. Tether binding increases the activity of SHP-1 by 900-fold through a binding-induced allosteric activation (20-fold) and a more significant increase in local substrate concentration (45-fold). The reach parameter indicates that this local substrate concentration is exquisitely sensitive to receptor clustering. We further show that truncation of the tether leads not only to a lower reach but also to lower binding and catalysis. This work establishes a new framework for studying tethered signaling processes and highlights the tether as a control parameter in clustered receptor signaling.

  4. Biophysical assay for tethered signaling reactions reveals tether-controlled activity for the phosphatase SHP-1

    PubMed Central

    Goyette, Jesse; Salas, Citlali Solis; Coker-Gordon, Nicola; Bridge, Marcus; Isaacson, Samuel A.; Allard, Jun; Dushek, Omer

    2017-01-01

    Tethered enzymatic reactions are ubiquitous in signaling networks but are poorly understood. A previously unreported mathematical analysis is established for tethered signaling reactions in surface plasmon resonance (SPR). Applying the method to the phosphatase SHP-1 interacting with a phosphorylated tether corresponding to an immune receptor cytoplasmic tail provides five biophysical/biochemical constants from a single SPR experiment: two binding rates, two catalytic rates, and a reach parameter. Tether binding increases the activity of SHP-1 by 900-fold through a binding-induced allosteric activation (20-fold) and a more significant increase in local substrate concentration (45-fold). The reach parameter indicates that this local substrate concentration is exquisitely sensitive to receptor clustering. We further show that truncation of the tether leads not only to a lower reach but also to lower binding and catalysis. This work establishes a new framework for studying tethered signaling processes and highlights the tether as a control parameter in clustered receptor signaling. PMID:28378014

  5. Synergy among manganese, nitrogen and carbon to improve the catalytic activity for oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Kang, Jian; Wang, Hui; Ji, Shan; Key, Julian; Wang, Rongfang

    2014-04-01

    A highly active electrocatalyst for oxygen reduction reaction, manganese modified glycine derivative-carbon (Mn-CNx), is synthesized by a two-step carbonizing process. X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy are used to characterize structure and morphology of the catalysts. Electrochemical tests show that Mn-CNx has higher catalytic activity for oxygen reduction reaction than CNx derived glycine and Mn modified Vulcan carbon. Moreover, the half-wave potential of Mn-CNx is only 12 mV lower than that of commercial Pt/C. Mn-CNx also has excellent durability to methanol crossover in alkaline solution, and thus provides a promising low cost, non-precious metal cathode catalyst for fuel cells.

  6. [Generalization of activation reaction extinction during consecutive stimulation of different parts of the brain].

    PubMed

    Kratin, Iu G; Andreeva, V N

    1978-01-01

    The process of extinction of the brain activation reactions ("arousal") was studied in chronic experiments on cats with implanted electrodes during repeated electrical stimulation of alternated points in the cortex and in the brain stem reticular formation. Extinction of the reactions achieved by stimulation of one point resulted in the loss of excitability both at this point and in other activating structures at different levels of the brain. The sequence of stimulated structures was of no importance. A possibility is suggested of development of a generalized inhibition in the neural net of the non-specific reticular system of the brain which may be inciated in any point of this system: in the brain stem, in the thalamus or in the cortex.

  7. Reaction of active uranium and thorium with aromatic carbonyls and pinacols in hydrocarbon solvents

    SciTech Connect

    Kahn, B.E.; Rieke, R.D.

    1988-02-01

    Highly reactive uranium and thorium metal powders have been prepared by reduction of the anhydrous metal(IV) chlorides in hydrocarbon solvents. The reduction employs the crystalline hydrocarbon-soluble reducing agent ((TMEDA)Li)/sub 2/(Nap) (TMEDA = N,N,N',N'-tetramethylethylenediamine, Nap = naphthalene). The resulting active metal powders have been shown to be extremely reactive with oxygen-containing compounds and have been used in the reductive coupling of aromatic ketones giving tetra-arylethylenes. Reactions with pinacols have given some mechanistic insight into the ketone coupling reaction. These finely divided metal powders activate very weakly acidic C-H bonds forming metal hydrides, which can be transferred to organic substrates.

  8. Integral Equation Calculation of Solvent Activation Free Energies for Electron and Proton Transfer Reactions

    DTIC Science & Technology

    1993-11-04

    6. AUTHOR(S) P.P. Schmidt Indrani Bhattacharya- Kodali and Gregory Voth 7. PERFORMING ORGANIZATION NAME(S) AND AODRESS(ES) 8. PERIORMING ORGANIZATION...13. ABSTRACT (Maimum 200 words) The extended reference interaction site method (RISM) integral equation theory is applied to calculate the solvent...Integral Equation Calculation of Solvent Activation Free Energies for Electron and Proton Transfer Reactions Indrani Bhattacharya- Kodali and Gregory A. Voth

  9. Boosting oxygen reduction/evolution reaction activities with layered perovskite catalysts.

    PubMed

    Chen, Dengjie; Wang, Jian; Zhang, Zhenbao; Shao, Zongping; Ciucci, Francesco

    2016-08-25

    Layered PrBaMn2O5+δ (H-PBM) was simply prepared by annealing pristine Pr0.5Ba0.5MnO3-δ in H2. The oxygen reduction/evolution reaction activities are remarkably enhanced by employing H-PBM. The improvement can be ascribed to the introduction of additional oxygen vacancies, an optimized eg filling of Mn ions, and the facile incorporation of oxygen into layered H-PBM.

  10. Polyclonal antibodies against the TLA1 protein also recognize with high specificity the D2 reaction center protein of PSII in the green alga Chlamydomonas reinhardtii.

    PubMed

    Mitra, Mautusi; Dewez, David; García-Cerdán, Jose Gines; Melis, Anastasios

    2012-04-01

    The Chlamydomonas reinhardtii DNA-insertional transformant truncated light-harvesting antenna 1 (tla1) mutant, helped identify the novel TLA1 gene (GenBank Accession # AF534570-71) as an important genetic determinant in the chlorophyll antenna size of photosynthesis. Down-regulation in the amount of the TLA1 23 kDa protein in the cell resulted in smaller chlorophyll antenna size for both photosystems (in Tetali et al. Planta 225:813-829, 2007). Specific polyclonal antibodies, raised against the recombinant TLA1 protein, showed a cross-reaction with the predicted 23 kDa TLA1 protein in C. reinhardtii protein extracts, but also showed a strong cross-reaction with a protein band migrating to 28.5 kDa. Questions of polymorphism, or posttranslational modification of the TLA1 protein were raised as a result of the unexpected 28.5 kDa cross-reaction. Work in this paper aimed to elucidate the nature of the unexpected 28.5 kDa cross-reaction, as this was deemed to be important in terms of the functional role of the TLA1 protein in the regulation of the chlorophyll antenna size of photosynthesis. Immuno-precipitation of the 28.5 kDa protein, followed by LC-mass spectrometry, showed amino acid sequences ascribed to the psbD/D2 reaction center protein of PSII. The common antigenic determinant between TLA1 and D2 was shown to be a stretch of nine conserved amino acids V-F-L(V)LP-GNAL in the C-terminus of the two proteins, constituting a high antigenicity "GNAL" domain. Antibodies raised against the TLA1 protein containing this domain recognized both the TLA1 and the D2 protein. Conversely, antibodies raised against the TLA1 protein minus the GNAL domain specifically recognized the 23 kDa TLA1 protein and failed to recognize the 28.5 kDa D2 protein. D2 antibodies raised against an oligopeptide containing this domain also cross-reacted with the TLA1 protein. It is concluded that the 28.5 kDa cross-reaction of C. reinhardtii protein extracts with antiTLA1 antibodies is due to

  11. Stable platinum nanoclusters on genomic DNA-graphene oxide with a high oxygen reduction reaction activity.

    PubMed

    Tiwari, Jitendra N; Nath, Krishna; Kumar, Susheel; Tiwari, Rajanish N; Kemp, K Christian; Le, Nhien H; Youn, Duck Hyun; Lee, Jae Sung; Kim, Kwang S

    2013-01-01

    Nanosize platinum clusters with small diameters of 2-4 nm are known to be excellent catalysts for the oxygen reduction reaction. The inherent catalytic activity of smaller platinum clusters has not yet been reported due to a lack of preparation methods to control their size (<2 nm). Here we report the synthesis of platinum clusters (diameter ≤1.4 nm) deposited on genomic double-stranded DNA-graphene oxide composites, and their high-performance electrocatalysis of the oxygen reduction reaction. The electrochemical behaviour, characterized by oxygen reduction reaction onset potential, half-wave potential, specific activity, mass activity, accelerated durability test (10,000 cycles) and cyclic voltammetry stability (10,000 cycles) is attributed to the strong interaction between the nanosize platinum clusters and the DNA-graphene oxide composite, which induces modulation in the electronic structure of the platinum clusters. Furthermore, we show that the platinum cluster/DNA-graphene oxide composite possesses notable environmental durability and stability, vital for high-performance fuel cells and batteries.

  12. Effects of subthalamic nucleus stimulation on characteristics of EMG activity underlying reaction time in Parkinson's disease.

    PubMed

    Kumru, Hatice; Summerfield, Christopher; Valldeoriola, Francesc; Valls-Solé, Josep

    2004-01-01

    We examined the effects of high-frequency deep brain stimulation of the subthalamic nucleus (STN-DBS) on characteristics of electromyographic (EMG) activity of the agonist muscle in 8 patients with Parkinson's disease (PD). Patients were examined during STN-DBS (ON), and 30 minutes after switching off both stimulators (OFF). They were asked to make a ballistic movement in paradigms of simple reaction time (SRT) and choice reaction time (CRT) tasks. Onset of movement (MOVonset) was measured as the latency of the initial displacement from baseline of the signal from an accelerometer attached to the dorsum of the hand. In the associated EMG activity, recorded from wrist extensor muscles, we measured onset latency (EMGonset), size of the first EMG burst (EMGsize), and number of EMG bursts (EMGbursts) counted between EMGonset and task execution. MOVonset and EMGonset were significantly shorter in ON than in OFF conditions in CRT. EMGsize was larger, EMGbursts were reduced, and peak of the acceleration profile was larger in ON compared with OFF conditions in both SRT and CRT. Our results indicate that STN-DBS induces a significant improvement in motor performance of reaction time tasks in PD patients. Such improvement is associated with a change in features of the EMG activity suggesting an increase in the excitability of the motor pathways engaged in ballistic movements.

  13. Nanoporous and highly active silicon carbide supported CeO₂-catalysts for the methane oxidation reaction.

    PubMed

    Hoffmann, Claudia; Biemelt, Tim; Lohe, Martin R; Rümmeli, Mark H; Kaskel, Stefan

    2014-01-29

    CeOx @SiO2 nanoparticles are used for the first time for the generation of porous SiC materials with tailored pore diameter in the mesopore range containing encapsulated and catalytically active CeO2 nanoparticles. The nanocasting approach with a preceramic polymer and subsequent pyrolysis is performed at 1300 °C, selective leaching of the siliceous part results in CeOx /SiC catalysts with remarkable characteristics like monodisperse, spherical pores and specific surface areas of up to 438 m(2) ·g(-1) . Porous SiC materials are promising supports for high temperature applications. The catalysts show excellent activities in the oxidation of methane with onset temperatures of the reaction 270 K below the onset of the homogeneous reaction. The synthesis scheme using core-shell particles is suited to functionalize silicon carbide with a high degree of stabilization of the active nanoparticles against sintering in the core of the template even at pyrolysis temperatures of 1300 °C rendering the novel synthesis principle as an attractive approach for a wide range of catalytic reactions.

  14. (100) facets of γ-Al2O3: the active surfaces for alcohol dehydration reactions

    SciTech Connect

    Kwak, Ja Hun; Mei, Donghai; Peden, Charles HF; Rousseau, Roger J.; Szanyi, Janos

    2011-05-01

    Temperature programmed desorption (TPD) of ethanol, and methanol dehydration reaction were studied on γ-Al2O3 in order to identify the catalytic active sites for alcohol dehydration reactions. Two high temperature (> 473 K) desorption features were observed following ethanol adsorption. Samples calcined at T≤473 K displayed a desorption feature in the 523-533 K temperature range, while those calcined at T ≥ 673 K showed a single desorption feature at 498 K. The switch from the high to low temperature ethanol desorption correlated well with the dehydroxylation of the (100) facets of γ-Al2O3 that was predicted at 550 K DFT calculations. Theoretical DFT simulations of the mechanism of dehydration. on clean and hydroxylated γ-Al2O3(100) surfaces, find that a concerted elimination of ethylene from an ethanol molecule chemisorbed at an Al3+ pentacoordinated site is the rate limiting step for catalytic cycle on both surfaces. Furthermore, titration of the pentacoordinate Al3+ sites on the (100) facets of γ-Al2O3 by BaO completely turned off the methanol dehydration reaction activity. These results unambiguously demonstrate that only the (100) facets on γ-Al2O3 are the catalytic active surfaces for alcohol dehydration.

  15. Rapamycin protects neurons from brain contusion-induced inflammatory reaction via modulation of microglial activation

    PubMed Central

    SONG, QI; XIE, DUJIANG; PAN, SHIYONG; XU, WEIJUN

    2015-01-01

    The inflammatory reaction is important in secondary injury following traumatic brain injury (TBI). Rapamycin has been demonstrated as a neuroprotective agent in a mouse model of TBI, however, there is a lack of data regarding the effects of rapamycin on the inflammatory reaction following TBI. Therefore, the present study was designed to assess the effects of treatment with rapamycin on inflammatory reactions and examine the possible involvement of microglial activation following TBI. Male imprinting control region mice were randomly divided into four groups: Sham group (n=23), TBI group (n=23), TBI + dimethyl sulfoxide (DMSO) group (n=31) and TBI + rapamycin group (n=31). Rapamycin was dissolved in DMSO (50 mg/ml) and injected 30 min after TBI (2 mg/Kg; intraperitoneally). A weight-drop model of TBI was induced, and the brain tissues were harvested 24 h after TBI. The findings indicated that the administration of rapamycin following TBI was associated with decreased levels of activated microglia and neuron degeneration at the peri-injury site, reduced levels of proinflammatory cytokines and increased neurobehavioral function, possibly mediated by inactivation of the mammalian target of rapamycin pathway. The results of the present study offer novel insight into the mechanisms responsible for the anti-neuroinflammatory effects of rapamycin, possibly involving the modulation of microglial activation. PMID:26458361

  16. Psychophysiological reactions during active and passive stress coping following smoking cessation.

    PubMed

    Hasenfratz, M; Bättig, K

    1991-01-01

    This study investigated the effects of 9 days' smoking abstinence on psychophysiological stress reactions. The subjects were 40 female smokers; 20 of them intended to give up smoking in the course of the study, whereas the remaining 20 had no such intention. A first session was carried out before, a second and a third during days 3 and 9 of abstinence. The nonabstainers were tested at corresponding intervals. Each session consisted of a 30-min stress-coping phase with relaxation phases before and after. While performing a rapid information processing task (RIP) the subjects had to sustain electrical shocks which were, according to instructions, but not in fact, either avoidable (active coping) or not (passive coping). Generally, the active coping instruction produced greater responses to the RIP task than did the passive coping instruction for heart rate, systolic and diastolic blood pressure but not for finger pulse amplitude, thus resembling a beta-adrenergic stimulation. RIP processing rate was not affected, but the response rate (total of hits and commission errors) was greater during active than during passive coping. However, none of these stress reactions differed between abstainers and nonabstainers. On the other hand, both heart rate and the craving to smoke decreased significantly in the abstainer group across the 9 days. Thus, it is concluded that a deprivation of 1 h, 3 or 9 days has no differential effect on physiological stress reactions.

  17. Active Learning and Student-centered Pedagogy Improve Student Attitudes and Performance in Introductory Biology

    PubMed Central

    Patel, Maya; Johnson, Erika; Weiss, Martha

    2009-01-01

    We describe the development and implementation of an instructional design that focused on bringing multiple forms of active learning and student-centered pedagogies to a one-semester, undergraduate introductory biology course for both majors and nonmajors. Our course redesign consisted of three major elements: 1) reordering the presentation of the course content in an attempt to teach specific content within the context of broad conceptual themes, 2) incorporating active and problem-based learning into every lecture, and 3) adopting strategies to create a more student-centered learning environment. Assessment of our instructional design consisted of a student survey and comparison of final exam performance across 3 years—1 year before our course redesign was implemented (2006) and during two successive years of implementation (2007 and 2008). The course restructuring led to significant improvement of self-reported student engagement and satisfaction and increased academic performance. We discuss the successes and ongoing challenges of our course restructuring and consider issues relevant to institutional change. PMID:19723815

  18. Reflection features in the Galactic Center and past activity of Sagittarius A*

    NASA Astrophysics Data System (ADS)

    Clavel, Maïca; Terrier, Regis; Goldwurm, Andrea; Morris, Mark; Jin, Chichuan; Ponti, Gabriele; Chuard, Dimitri

    2016-07-01

    X-ray observations carried out over the past two decades have captured an increasing number of reflection features within the molecular clouds located in the inner regions of our Galaxy. The intensity of these structures along with the correlated variations which are detected over the entire central molecular zone are strong evidence that this diffuse emission is created by the past activity of the supermassive black hole at the Galactic center, Sagittarius A*. In particular, within the last centuries, Sgr A* is likely to have experienced several short outbursts during which the black hole was at least a million times brighter than today. However, the precise description of the corresponding past catastrophic events is difficult to assess, mainly because the properties of the reflection features that they create while propagating away from Sgr A* depend on the line-of-sight distance, the geometry, and the size of the reflecting clouds, all of which are poorly known. I will review the different attempts to reconstruct Sgr A*'s past activity from the constraints obtained through the observation of the reflection features in the Galactic center, including the current Chandra monitoring.

  19. Activity of daptomycin against staphylococci collected from bloodstream infections in Spanish medical centers.

    PubMed

    Picazo, Juan J; Betriu, Carmen; Culebras, Esther; Rodríguez-Avial, Iciar; Gómez, María; López, Fátima

    2009-08-01

    We used the broth microdilution method to determine the MICs of daptomycin and 13 comparator agents against 319 methicillin-susceptible Staphylococcus aureus isolates, 201 methicillin-resistant S. aureus (MRSA) isolates, and 183 coagulase-negative staphylococci (CoNS). Isolates were consecutively collected from bloodstream infections in 39 Spanish medical centers during a 3-month period (March through May 2008). Among MRSA, 1 isolate with intermediate susceptibility to vancomycin and 6 isolates resistant to linezolid were found. Nonsusceptibility to teicoplanin was detected in 3.9% of CoNS. Daptomycin was highly active against the staphylococcal blood isolates tested-all were inhibited at the daptomycin susceptibility breakpoint of < or = 1 microg/mL. Daptomycin retained its activity against the isolates that were resistant to teicoplanin or linezolid, or that had reduced susceptibility to vancomycin. These data suggest that daptomycin could be useful for the treatment of bloodstream infections caused by staphylococci.

  20. Overview of free-piston Stirling SP-100 activities at the NASA Lewis Research Center

    NASA Technical Reports Server (NTRS)

    Slaby, J. G.

    1986-01-01

    An overview of the National Aeronautics and Space Administration (NASA) Lewis Research Center (LeRC) SP-100 free-piston Stirling engine activities is presented. These activities are being conducted in support of the Department of Defense (DOD), Department of Energy (DOE), and NASA. The space-power technology effort, under SP-100, addresses the status of the 25 kWe Space Power Demonstrator Engine (SPDE). Another facet of the SP-100 project covers the status of an endurance test. Dynamic balancing of the SPDE engine is discussed along with a summary covering the parametric results of a study showing the relationship between power-converter specific weight and efficiency both as a function of Stirling engine heater to cooler temperature ratio. Design parameters and conceptual design features are presented for a 25 kWe, single-cylinder free-piston Stirling space-power converter. And finally, a description of a hydrodynamic gas bearing concept is presented.