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Sample records for additional functional groups

  1. Group Sparse Additive Models

    PubMed Central

    Yin, Junming; Chen, Xi; Xing, Eric P.

    2016-01-01

    We consider the problem of sparse variable selection in nonparametric additive models, with the prior knowledge of the structure among the covariates to encourage those variables within a group to be selected jointly. Previous works either study the group sparsity in the parametric setting (e.g., group lasso), or address the problem in the nonparametric setting without exploiting the structural information (e.g., sparse additive models). In this paper, we present a new method, called group sparse additive models (GroupSpAM), which can handle group sparsity in additive models. We generalize the ℓ1/ℓ2 norm to Hilbert spaces as the sparsity-inducing penalty in GroupSpAM. Moreover, we derive a novel thresholding condition for identifying the functional sparsity at the group level, and propose an efficient block coordinate descent algorithm for constructing the estimate. We demonstrate by simulation that GroupSpAM substantially outperforms the competing methods in terms of support recovery and prediction accuracy in additive models, and also conduct a comparative experiment on a real breast cancer dataset.

  2. Functional Generalized Additive Models.

    PubMed

    McLean, Mathew W; Hooker, Giles; Staicu, Ana-Maria; Scheipl, Fabian; Ruppert, David

    2014-01-01

    We introduce the functional generalized additive model (FGAM), a novel regression model for association studies between a scalar response and a functional predictor. We model the link-transformed mean response as the integral with respect to t of F{X(t), t} where F(·,·) is an unknown regression function and X(t) is a functional covariate. Rather than having an additive model in a finite number of principal components as in Müller and Yao (2008), our model incorporates the functional predictor directly and thus our model can be viewed as the natural functional extension of generalized additive models. We estimate F(·,·) using tensor-product B-splines with roughness penalties. A pointwise quantile transformation of the functional predictor is also considered to ensure each tensor-product B-spline has observed data on its support. The methods are evaluated using simulated data and their predictive performance is compared with other competing scalar-on-function regression alternatives. We illustrate the usefulness of our approach through an application to brain tractography, where X(t) is a signal from diffusion tensor imaging at position, t, along a tract in the brain. In one example, the response is disease-status (case or control) and in a second example, it is the score on a cognitive test. R code for performing the simulations and fitting the FGAM can be found in supplemental materials available online.

  3. Addition of surfactants in ozonated water cleaning for the suppression of functional group formation and particle adhesion on the SiO2 surface

    NASA Astrophysics Data System (ADS)

    Yang, Jahyun; Im, Kyungtaek; Lim, Sangwoo

    2011-04-01

    Various kinds of surfactants were added to a cleaning solution and deionized (DI) water, and their effect on the suppression of organic function group formation and particle adhesion to a SiO2 surface was analyzed using multi-internal reflection Fourier transform infrared spectroscopy. The results implied that attached organic functional groups are affected by the chemical structure of a surfactant in DI water. Furthermore, the addition of anionic glycolic acid ethoxylate 4-tert-butylphenyl ether (GAE4E) is the most effective in terms of preventing organic group attachment and particle adhesion to the SiO2 surface, whether it was added to the cleaning solution or post-cleaning rinse water, with or without polystyrene latex particles. Moreover, it was possible to completely prevent particle adhesion to the SiO2 surface with the proper addition of GAE4E in DIO3 solution.

  4. Water makes the difference: rearrangement of water solvation layer triggers non-additivity of functional group contributions in protein-ligand binding.

    PubMed

    Biela, Adam; Betz, Michael; Heine, Andreas; Klebe, Gerhard

    2012-08-01

    The binding of four congeneric peptide-like thermolysin inhibitors has been studied by high-resolution crystal structure analysis and isothermal titration calorimetry. The ligands differ only by a terminal carboxylate and/or methyl group. A surprising non-additivity of functional group contributions for the carboxylate and/or methyl groups is detected. Adding the methyl first and then the carboxylate group results in a small Gibbs free energy increase and minor enthalpy/entropy partitioning for the first modification, whereas the second involves a strong affinity increase combined with large enthalpy/entropy changes. However, first adding the carboxylate and then the methyl group yields reverse effects: the acidic group attachment now causes minor effects, whereas the added methyl group provokes large changes. As all crystal structures show virtually identical binding modes, affinity changes are related to rearrangements of the first solvation layer next to the S(2)' pocket. About 20-25 water molecules are visible next to the studied complexes. The added COO(-) groups perturb the local water network in both carboxylated complexes, and the attached methyl groups provide favorable interaction sites for water molecules. Apart from one example, a contiguously connected water network between protein and ligand functional groups is observed in all complexes. In the complex with the carboxylated ligand, which still lacks the terminal methyl group, the water network is unfavorably ruptured. This results in a surprising thermodynamic signature showing only a minor affinity increase upon COO(-) group attachment. Because the further added methyl group provides a favorable interaction site for water, the network can be reestablished, and a strong affinity increase with a large enthalpy/entropy signature is then detected.

  5. Group additivity calculation of the standard molal thermodynamic properties of aqueous amino acids, polypeptides and unfolded proteins as a function of temperature, pressure and ionization state

    NASA Astrophysics Data System (ADS)

    Dick, J. M.; Larowe, D. E.; Helgeson, H. C.

    2005-10-01

    Thermodynamic calculation of the chemical speciation of proteins and the limits of protein metastability affords a quantitative understanding of the biogeochemical constraints on the distribution of proteins within and among different organisms and chemical environments. These calculations depend on accurate determination of the ionization states and standard molal Gibbs free energies of proteins as a function of temperature and pressure, which are not generally available. Hence, to aid predictions of the standard molal thermodynamic properties of ionized proteins as a function of temperature and pressure, calculated values are given below of the standard molal thermodynamic properties at 25°C and 1 bar and the revised Helgeson-Kirkham-Flowers equations of state parameters of the structural groups comprising amino acids, polypeptides and unfolded proteins. Group additivity and correlation algorithms were used to calculate contributions by ionized and neutral sidechain and backbone groups to the standard molal Gibbs free energy (Δ G°), enthalpy (Δ H°), entropy (S°), isobaric heat capacity (C°P), volume (V°) and isothermal compressibility (κ°T) of multiple reference model compounds. Experimental values of C°P, V° and κ°T at high temperature were taken from the recent literature, which ensures an internally consistent revision of the thermodynamic properties and equations of state parameters of the sidechain and backbone groups of proteins, as well as organic groups. As a result, Δ G°, Δ H°, S° C°P, V° and κ°T of unfolded proteins in any ionization state can be calculated up to T~-300°C and P~-5000 bars. In addition, the ionization states of unfolded proteins as a function of not only pH, but also temperature and pressure can be calculated by taking account of the degree of ionization of the sidechain and backbone groups present in the sequence. Calculations of this kind represent a first step in the prediction of chemical affinities of many

  6. Addition polyimide adhesives containing various end groups

    NASA Technical Reports Server (NTRS)

    Saint Clair, A. K.; Saint Clair, T. L.

    1982-01-01

    Addition polyimode oligomers have been synthesized from 3,3 prime, 4,4 prime-benzophenone tetracarboxylic acid dianhydride and 3,3 prime-methylenedianiline using a variety of latent crosslinking groups as end-caps. The nominal 1300 molecular weight imide prepolymers were isolated and characterized for solubility in amide, chlorinated and ether solvents, melt-flow and cure properties, glass transition temperature, and thermal stability on heating in an air atmosphere. Adhesive strengths of the polyimides were obtained both at ambient and elevated temperatures before and after aging at 232 C. Properties of the novel addition polyimides were compared to a known nadic end-capped adhesive, LARC-13.

  7. Functional Group Analysis.

    ERIC Educational Resources Information Center

    Smith, Walter T., Jr.; Patterson, John M.

    1984-01-01

    Literature on analytical methods related to the functional groups of 17 chemical compounds is reviewed. These compounds include acids, acid azides, alcohols, aldehydes, ketones, amino acids, aromatic hydrocarbons, carbodiimides, carbohydrates, ethers, nitro compounds, nitrosamines, organometallic compounds, peroxides, phenols, silicon compounds,…

  8. Functional group analysis

    SciTech Connect

    Smith, W.T. Jr.; Patterson, J.M.

    1986-04-01

    Analytical methods for functional group analysis are reviewed. Literature reviewed is from the period of December 1983 through November 1985 and presents methods for determining the following compounds: acids, acid halides, active hydrogen, alcohols, aldehydes, ketones, amides, amines, amino acids, anhydrides, aromatic hydrocarbons, azo compounds, carbohydrates, chloramines, esters, ethers, halogen compounds, hydrazines, isothiocyanates, nitro compounds, nitroso compounds, organometallic compounds, oxiranes, peroxides, phenols, phosphorus compounds, quinones, silicon compounds, sulfates, sulfonyl chlorides, thioamides, thiols, and thiosemicarbazones. 150 references.

  9. Cluster functional renormalization group

    NASA Astrophysics Data System (ADS)

    Reuther, Johannes; Thomale, Ronny

    2014-01-01

    Functional renormalization group (FRG) has become a diverse and powerful tool to derive effective low-energy scattering vertices of interacting many-body systems. Starting from a free expansion point of the action, the flow of the RG parameter Λ allows us to trace the evolution of the effective one- and two-particle vertices towards low energies by taking into account the vertex corrections between all parquet channels in an unbiased fashion. In this work, we generalize the expansion point at which the diagrammatic resummation procedure is initiated from a free UV limit to a cluster product state. We formulate a cluster FRG scheme where the noninteracting building blocks (i.e., decoupled spin clusters) are treated exactly, and the intercluster couplings are addressed via RG. As a benchmark study, we apply our cluster FRG scheme to the spin-1/2 bilayer Heisenberg model (BHM) on a square lattice where the neighboring sites in the two layers form the individual two-site clusters. Comparing with existing numerical evidence for the BHM, we obtain reasonable findings for the spin susceptibility, the spin-triplet excitation energy, and quasiparticle weight even in coupling regimes close to antiferromagnetic order. The concept of cluster FRG promises applications to a large class of interacting electron systems.

  10. Characterizing neuromorphologic alterations with additive shape functionals

    NASA Astrophysics Data System (ADS)

    Barbosa, M. S.; Costa, L. Da F.; Bernardes, E. S.; Ramakers, G.; van Pelt, J.

    2004-01-01

    The complexity of a neuronal cell shape is known to be related to its function. Specifically, among other indicators, a decreased complexity in the dendritic trees of cortical pyramidal neurons has been associated with mental retardation. In this paper we develop a procedure to address the characterization of morphological changes induced in cultured neurons by over-expressing a gene involved in mental retardation. Measures associated with the multiscale connectivity, an additive image functional, are found to give a reasonable separation criterion between two categories of cells. One category consists of a control group and two transfected groups of neurons, and the other, a class of cat ganglionary cells. The reported framework also identified a trend towards lower complexity in one of the transfected groups. Such results establish the suggested measures as an effective descriptors of cell shape.

  11. Functional Group Analysis.

    ERIC Educational Resources Information Center

    Smith, Walter T., Jr.; Patterson, John M.

    1980-01-01

    Discusses analytical methods selected from current research articles. Groups information by topics of general interest, including acids, aldehydes and ketones, nitro compounds, phenols, and thiols. Cites 97 references. (CS)

  12. Additives

    NASA Technical Reports Server (NTRS)

    Smalheer, C. V.

    1973-01-01

    The chemistry of lubricant additives is discussed to show what the additives are chemically and what functions they perform in the lubrication of various kinds of equipment. Current theories regarding the mode of action of lubricant additives are presented. The additive groups discussed include the following: (1) detergents and dispersants, (2) corrosion inhibitors, (3) antioxidants, (4) viscosity index improvers, (5) pour point depressants, and (6) antifouling agents.

  13. 32 CFR 2003.15 - Additional functions.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... President through the National Security Advisor, the ISCAP performs such additional advisory functions as... National Defense Other Regulations Relating to National Defense INFORMATION SECURITY OVERSIGHT OFFICE, NATIONAL ARCHIVES AND RECORDS ADMINISTRATION INTERAGENCY SECURITY CLASSIFICATION APPEALS PANEL...

  14. 32 CFR 2003.15 - Additional functions.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... President through the National Security Advisor, the ISCAP performs such additional advisory functions as... National Defense Other Regulations Relating to National Defense INFORMATION SECURITY OVERSIGHT OFFICE, NATIONAL ARCHIVES AND RECORDS ADMINISTRATION INTERAGENCY SECURITY CLASSIFICATION APPEALS PANEL...

  15. Additive Bilingualism, Schooling, and Special Education: A Minority Group Perspective.

    ERIC Educational Resources Information Center

    Landry, R.

    1987-01-01

    The effect of schooling on the acquisition of an additive type of bilingualism is examined, focusing on additive bilingualism's relation to the ethnolinguistic vitality of linguistic groups and contributions of individual networks of linguistic contacts. A special and regular education merger without domination by a single cultural perspective is…

  16. A practical catalytic asymmetric addition of alkyl groups to ketones.

    PubMed

    García, Celina; LaRochelle, Lynne K; Walsh, Patrick J

    2002-09-18

    Many catalysts will promote the asymmetric addition of alkylzinc reagents to aldehydes. In contrast, there are no reports of additions to ketones that are both general and highly enantioselective. We describe herein a practical catalytic asymmetric addition of ethyl groups to ketones. The catalyst is derived from reaction of camphor sulfonyl chloride and trans-1,2-diaminocyclohexane. The resulting diketone is reduced with NaBH4 to give the C2-symmetric exo diastereomer. Use of this ligand with titanium tetraisopropoxide and dialkylzinc at room temperature results in enantioselective addition of the alkyl group to the ketone. The resulting tertiary alcohols are isolated with high enantiomeric excess (all cases give greater than 87% ee, except one). The reaction has been run with 37 mmol (5 g) 3-methylacetophenone and 2 mol % catalyst to afford 73% yield of the resulting tertiary alcohol with 99% ee.

  17. Polyetherurethane oligomers with aldehyde groups as additives for lubricating oils

    SciTech Connect

    Nikolaev, V.N.; Abramov, E.G.; Tenyushev, A.I.

    1995-01-01

    Polyetherurethane oligomers with aldehyde groups, which we synthesized from polyoxypropylene diols (molecular weight 500, 1000, 1500, 2000, or 3000) with toluene diisocyanate and salicylaldehyde, are of interest as additives for lubricating oils. The effects of these oligomers on the service properties and physicochemical characteristics of lubricating oils were investigated by methods prreviously described. As the lube base stocks we used castor oil, a polyoxypropylene diol and a polyethoxysiloxane. The oligomers are readily soluble in organic solvents and in the lube base stocks, and their solutions are stable during storage and use. We found that the optimal concentration of oligomers is 5%, providing the best lubricating properties, in particular the best antiwear properties.

  18. A Functional Analytic Approach to Group Psychotherapy

    ERIC Educational Resources Information Center

    Vandenberghe, Luc

    2009-01-01

    This article provides a particular view on the use of Functional Analytical Psychotherapy (FAP) in a group therapy format. This view is based on the author's experiences as a supervisor of Functional Analytical Psychotherapy Groups, including groups for women with depression and groups for chronic pain patients. The contexts in which this approach…

  19. A Comparison of Group-Oriented Contingencies for Addition Fluency

    ERIC Educational Resources Information Center

    Gross, Thomas J.; Duhon, Gary J.; Shutte, Greg; Rowland, Julie E.

    2016-01-01

    Math fact fluency is critical for understanding complex mathematics. Explicit timing interventions have shown promise for improving math fluency, and they may benefit from being paired with group-oriented contingencies. Further, investigations of independent and dependent group-oriented contingencies would help to identify their relative…

  20. Relating Functional Groups to the Periodic Table

    ERIC Educational Resources Information Center

    Struyf, Jef

    2009-01-01

    An introduction to organic chemistry functional groups and their ionic variants is presented. Functional groups are ordered by the position of their specific (hetero) atom in the periodic table. Lewis structures are compared with their corresponding condensed formulas. (Contains 5 tables.)

  1. 34 CFR 300.308 - Additional group members.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Educational Placements Additional Procedures for Identifying Children with Specific Learning Disabilities... learning disability is a child with a disability as defined in § 300.8, must be made by the child's parents... examinations of children, such as a school psychologist, speech-language pathologist, or remedial...

  2. 34 CFR 300.308 - Additional group members.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... Educational Placements Additional Procedures for Identifying Children with Specific Learning Disabilities... learning disability is a child with a disability as defined in § 300.8, must be made by the child's parents...) If the child does not have a regular teacher, a regular classroom teacher qualified to teach a...

  3. 34 CFR 300.308 - Additional group members.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Educational Placements Additional Procedures for Identifying Children with Specific Learning Disabilities... learning disability is a child with a disability as defined in § 300.8, must be made by the child's parents...) If the child does not have a regular teacher, a regular classroom teacher qualified to teach a...

  4. Silsesquioxane nanoparticles with reactive internal functional groups

    NASA Astrophysics Data System (ADS)

    Brozek, Eric M.; Washton, Nancy M.; Mueller, Karl T.; Zharov, Ilya

    2017-02-01

    A series of silsesquioxane nanoparticles containing reactive internal organic functionalities throughout the entire particle body have been synthesized using a surfactant-free method with organosilanes as the sole precursors and a base catalyst. The organic functional groups incorporated are vinyl, allyl, mercapto, cyanoethyl, and cyanopropyl groups. The sizes and morphologies of the particles were characterized using SEM and nitrogen adsorption, while the compositions were confirmed using TGA, FT-IR, solid state NMR, and elemental analysis. The accessibility and reactivity of the functional groups inside the particles were demonstrated by performing bromination and reduction reactions in the interior of the particles.

  5. Group entropies, correlation laws, and zeta functions

    NASA Astrophysics Data System (ADS)

    Tempesta, Piergiulio

    2011-08-01

    The notion of group entropy is proposed. It enables the unification and generaliztion of many different definitions of entropy known in the literature, such as those of Boltzmann-Gibbs, Tsallis, Abe, and Kaniadakis. Other entropic functionals are introduced, related to nontrivial correlation laws characterizing universality classes of systems out of equilibrium when the dynamics is weakly chaotic. The associated thermostatistics are discussed. The mathematical structure underlying our construction is that of formal group theory, which provides the general structure of the correlations among particles and dictates the associated entropic functionals. As an example of application, the role of group entropies in information theory is illustrated and generalizations of the Kullback-Leibler divergence are proposed. A new connection between statistical mechanics and zeta functions is established. In particular, Tsallis entropy is related to the classical Riemann zeta function.

  6. Nonlinear responses in salt marsh functioning to increased nitrogen addition.

    PubMed

    Vivanco, Lucía; Irvine, Irina C; Martiny, Jennifer B H

    2015-04-01

    Salt marshes provide storm protection to shorelines, sequester carbon (C), and mitigate coastal eutrophication. These valuable coastal ecosystems are confronted with increasing nitrogen (N) inputs from anthropogenic sources, such as agricultural runoff, wastewater, and atmospheric deposition. To inform predictions of salt marsh functioning and sustainability in the future, we characterized the response of a variety of plant, microbial, and sediment responses to a seven-level gradient of N addition in three Californian salt marshes after 7 and 14 months of N addition. The marshes showed variable responses to the experimental N gradient that can be grouped as neutral (root biomass, sediment respiration, potential carbon mineralization, and potential net nitrification), linear (increasing methane flux, decreasing potential net N mineralization, and increasing sediment inorganic N), and nonlinear (saturating aboveground plant biomass and leaf N content, and exponentially increasing sediment inorganic and organic N). The three salt marshes showed quantitative differences in most ecosystem properties and processes rates; however, the form of the response curves to N addition were generally consistent across the three marshes, indicating that the responses observed may be applicable to other marshes in the region. Only for sediment properties (inorganic and organic N pool) did the shape of the response differ significantly between marshes. Overall, the study suggests salt marshes are limited in their ability to sequester C and N with future increases in N, even without further losses in marsh area.

  7. Identifying copepod functional groups from species functional traits

    PubMed Central

    Benedetti, Fabio; Gasparini, Stéphane; Ayata, Sakina-Dorothée

    2016-01-01

    We gathered information on the functional traits of the most representative copepod species in the Mediterranean Sea. Our database includes 191 species described by 7 traits encompassing diverse ecological functions: minimal and maximal body length, trophic group, feeding type, spawning strategy, diel vertical migration and vertical habitat. Cluster analysis in the functional trait space revealed that Mediterranean copepods can be separated into groups with distinct ecological roles. PMID:26811565

  8. Functional Group Chemistry (by James R. Hanson)

    NASA Astrophysics Data System (ADS)

    Karty, Joel M.

    2002-06-01

    Given its density and brevity and the apparent requirement of previous organic chemistry knowledge, Functional Group Chemistry is inappropriate as a stand-alone text for first-year organic students. It is also difficult to imagine using it as a supplement to a traditional textbook, since the textbook would presumably provide the same material in greater depth and with better clarity. The end-of-chapter problems in Functional Group Chemistry, however, would provide excellent exam and supplemental homework questions, and would be appropriate given the greater emphasis on reaction mechanisms in the traditional textbook. Perhaps the best use for Functional Group Chemistry, then, is for students returning after having had a year of organic chemistry, either for a quick reference, or for an in-depth review in studying for a standardized exam.

  9. Some new addition formulae for Weierstrass elliptic functions

    PubMed Central

    Eilbeck, J. Chris; England, Matthew; Ônishi, Yoshihiro

    2014-01-01

    We present new addition formulae for the Weierstrass functions associated with a general elliptic curve. We prove the structure of the formulae in n-variables and give the explicit addition formulae for the 2- and 3-variable cases. These new results were inspired by new addition formulae found in the case of an equianharmonic curve, which we can now observe as a specialization of the results here. The new formulae, and the techniques used to find them, also follow the recent work for the generalization of Weierstrass functions to curves of higher genus. PMID:25383018

  10. Antibiotic inhibition of group I ribozyme function.

    PubMed

    von Ahsen, U; Davies, J; Schroeder, R

    1991-09-26

    The discovery of catalytically active RNA has provided the basis for the evolutionary concept of an RNA world. It has been proposed that during evolution the functions of ancient catalytic RNA were modulated by low molecular weight effectors, related to antibiotics, present in the primordial soup. Antibiotics and RNA may have coevolved in the formation of the modern ribosome. Here we report that a set of aminoglycoside antibiotics, which are known to interact with the decoding region of the 16S ribosomal RNA of Escherichia coli, inhibit the second step of splicing of the T4 phage-derived td intron. Thus catalytic RNA seems to interact not only with a mononucleotide and an amino acid, but also with another class of biomolecules, the sugars. Splicing of other group I introns but not group II introns was inhibited. The similarity in affinity and specificity of these antibiotics for group I introns and rRNAs may result from recognition of evolutionarily conserved structures.

  11. Hyperbolic tangential function-based progressive addition lens design.

    PubMed

    Qiu, Gufeng; Cui, Xudong

    2015-12-10

    The diopter distribution is key to the successful design of a progressive addition lens. A hyperbolic tangential function is then introduced to describe well the desired diopter distribution on the lens. Simulation and fabrication show that the astigmia on the whole surface is very close to the addition, exhibiting superior performance than that of currently used high-order polynomials and cosine functions. Our investigations found that once the diopter distribution design is reasonable, both the direct and indirect methods of constructing a progressive addition lens can give consistent results. With this function we are able to effectively control the design of critical areas, the position, sizes of far-view and near-view zones, as well as the channel of the lens. This study would provide an efficient way to customize different progressive lenses not only for presbyopia, but also for anti-fatigue, office progressive usages, etc.

  12. Functional renormalization group in Floquet space

    NASA Astrophysics Data System (ADS)

    Eissing, Anna Katharina; Meden, Volker; Kennes, Dante Marvin

    2016-12-01

    We present an extension of the functional renormalization group to Floquet space, which enables us to treat the long time behavior of interacting time periodically driven quantum dots. It is one of its strength that the method is neither bound to small driving amplitudes nor to small driving frequencies, i.e., very general time periodic signals can be considered. It is applied to the interacting resonant level model, a prototype model of a spinless, fermionic quantum dot. The renormalization in several setups with different combinations of time periodic parameters is studied, where the numerical results are complemented by analytic expressions for the renormalization in the limit of small driving amplitude. We show how the driving frequency acts as an infrared cutoff of the underlying renormalization group flow which manifests in novel power laws. We utilize the tunability of the effective reservoir distribution function in a periodically driven onsite energy setup to show how its shape is directly reflected in the renormalization group flow. This allows us to flexibly tune the power-law renormalization generically encountered in quantum dot structures. Finally, an in-phase quantum pump as well as a single parameter pump are investigated in the whole regime of driving frequency, demonstrating that the new power law in the driving frequency is reflected in the mean current of the latter.

  13. Covalently functionalized hexagonal boron nitride nanosheets by nitrene addition.

    PubMed

    Sainsbury, Toby; Satti, Amro; May, Peter; O'Neill, Arlene; Nicolosi, Valeria; Gun'ko, Yurii K; Coleman, Jonathan N

    2012-08-27

    The covalent functionalization of exfoliated hexagonal boron nitride (h-BN) nanosheets by nitrene addition is described. Integration of functionalized h-BN nanosheets within a polycarbonate matrix is demonstrated and was found to afford significant increases in mechanical properties. This integration methodology was further extended by the covalent modification of the h-BN nanosheets with polymer chains of a polycarbonate analogue, and the integration of the polymer modified h-BN within the polymer matrix.

  14. Side Group Addition to the PAH Coronene by UV Photolysis in Cosmic Ice Analogs

    NASA Technical Reports Server (NTRS)

    Bernstein, Max P.; Elsila, Jamie E.; Dworkin, Jason P.; Sandford, Scott A.; Allamandola, Louis J.; Zare, Richard N.; DeVincenzi, D. (Technical Monitor)

    2002-01-01

    Ultraviolet photolysis of various ice mixtures at low temperature and pressure caused the addition of amino (-NH2), methyl (-CH3), methoxy (-OCH3), and cyano (-CN) functional groups to the polycyclic aromatic hydrocarbon (PAH) coronene (C22H12). The implications of these results for interstellar and meteoritic chemistry are discussed. Previously only simple PAH photo-oxidation had been reported. This work represents the first experimental evidence that ice photochemistry may have contributed to aromatics bearing carbon and nitrogen containing side groups that are detected in primitive meteorites and interplanetary dust particles. Furthermore, these results suggest a wider range of modified PAHs should be expected in interstellar lees and materials predating solar system formation.

  15. Catalytic enantioselective 1,6-conjugate additions of propargyl and allyl groups.

    PubMed

    Meng, Fanke; Li, Xiben; Torker, Sebastian; Shi, Ying; Shen, Xiao; Hoveyda, Amir H

    2016-09-15

    Conjugate (or 1,4-) additions of carbanionic species to α,β-unsaturated carbonyl compounds are vital to research in organic and medicinal chemistry, and there are several chiral catalysts that facilitate the catalytic enantioselective additions of nucleophiles to enoates. Nonetheless, catalytic enantioselective 1,6-conjugate additions are uncommon, and ones that incorporate readily functionalizable moieties, such as propargyl or allyl groups, into acyclic α,β,γ,δ-doubly unsaturated acceptors are unknown. Chemical transformations that could generate a new bond at the C6 position of a dienoate are particularly desirable because the resulting products could then be subjected to further modifications. However, such reactions, especially when dienoates contain two equally substituted olefins, are scarce and are confined to reactions promoted by a phosphine-copper catalyst (with an alkyl Grignard reagent, dialkylzinc or trialkylaluminium compounds), a diene-iridium catalyst (with arylboroxines), or a bisphosphine-cobalt catalyst (with monosilyl-acetylenes). 1,6-Conjugate additions are otherwise limited to substrates where there is full substitution at the C4 position. It is unclear why certain catalysts favour bond formation at C6, and-although there are a small number of catalytic enantioselective conjugate allyl additions-related 1,6-additions and processes involving a propargyl unit are non-existent. Here we show that an easily accessible organocopper catalyst can promote 1,6-conjugate additions of propargyl and 2-boryl-substituted allyl groups to acyclic dienoates with high selectivity. A commercially available allenyl-boron compound or a monosubstituted allene may be used. Products can be obtained in up to 83 per cent yield, >98:2 diastereomeric ratio (for allyl additions) and 99:1 enantiomeric ratio. We elucidate the mechanistic details, including the origins of high site selectivity (1,6- versus 1,4-) and enantioselectivity as a function of the catalyst

  16. Catalytic enantioselective 1,6-conjugate additions of propargyl and allyl groups

    PubMed Central

    Meng, Fanke; Li, Xiben; Torker, Sebastian; Shi, Ying; Shen, Xiao; Hoveyda, Amir H.

    2016-01-01

    Conjugate (or 1,4-) additions of carbanionic species to α,β-unsaturated carbonyl compounds are vital to research in organic and medicinal chemistry, and there are several known chiral catalysts that facilitate the catalytic enantioselective additions of nucleophiles to enoates1. However, catalytic enantioselective 1,6-conjugate additions are uncommon, and ones that are able to incorporate readily functionalizable moieties, such as propargyl or allyl groups, into acyclic α,β,γ,δ-doubly unsaturated acceptors are unknown2. Chemical transformations that could generate a new bond at the C6 position of a dienoate are particularly desirable, as the resulting products would be subjected to further modifications; such reactions, especially when dienoates contain two equally substituted olefins, are scarce3 and are confined to reactions promoted by a phosphine–copper (with alkyl Grignard4,5, dialkylzinc or trialkylaluminum compounds6,7), a diene–iridium (with arylboroxines)8,9, and a bisphosphine–cobalt catalyst (with monosilyl-acetylenes)10. 1,6-conjugate additions are otherwise limited to substrates where there is full substitution at C411. It is not clear why certain catalysts favor bond formation at C6, and – while there are a small number of catalytic enantioselective conjugate allyl additions12,13,14,15 – related 1,6-additions and processes involving a propargyl unit are non-existent. In this manuscript, we show that an easily accessible organocopper catalyst can promote 1,6-conjugate additions of propargyl and 2-boryl-substituted allyl groups to acyclic dienoates with high selectivity. A commercially available allenylboron compound or a monosubstituted allene may be used. Products can be obtained in up to 83 percent yield, >98 percent diastereo- (for allyl additions) and 99:1 enantiomeric ratio. Mechanistic details, including the origins of high site- (1,6- versus 1,4-) and enantioselectivity as a function of the catalyst structure and reaction type

  17. Functional group-selective adsorption using scanning tunneling microscopy.

    PubMed

    Min, Young Hwan; Park, Eun Hee; Kim, Do Hwan; Kim, Sehun

    2012-04-24

    In this study, we selectively enhanced two types of adsorption of 3-mercaptoisobutyric acid on a Ge(100) surface by using the tunneling electrons from an STM and the catalytic effect of an STM tip. 3-Mercaptoisobutyric acid has two functional groups: a carboxylic acid group at one end of the molecule and a thiol group at the other end. It was found that the adsorption occurring through the carboxylic acid group was selectively enhanced by the application of electrons tunneling between an STM tip and the surface. Using this enhancement, it was possible to make thiol group-terminated surfaces at any desired location. In addition, via the use of a tungsten STM tip coated with a tungsten oxide (WO(3)) layer, we selectively catalyzed the adsorption through the thiol group. Using this catalysis, it was possible to generate carboxylic acid group-terminated surfaces at any desired location. This functional group-selective adsorption using STM could be applied in positive lithographic methods to produce semiconductor substrates terminated by desired functional groups.

  18. Catalytic enantioselective 1,6-conjugate additions of propargyl and allyl groups

    NASA Astrophysics Data System (ADS)

    Meng, Fanke; Li, Xiben; Torker, Sebastian; Shi, Ying; Shen, Xiao; Hoveyda, Amir H.

    2016-09-01

    Conjugate (or 1,4-) additions of carbanionic species to α,β-unsaturated carbonyl compounds are vital to research in organic and medicinal chemistry, and there are several chiral catalysts that facilitate the catalytic enantioselective additions of nucleophiles to enoates. Nonetheless, catalytic enantioselective 1,6-conjugate additions are uncommon, and ones that incorporate readily functionalizable moieties, such as propargyl or allyl groups, into acyclic α,β,γ,δ-doubly unsaturated acceptors are unknown. Chemical transformations that could generate a new bond at the C6 position of a dienoate are particularly desirable because the resulting products could then be subjected to further modifications. However, such reactions, especially when dienoates contain two equally substituted olefins, are scarce and are confined to reactions promoted by a phosphine-copper catalyst (with an alkyl Grignard reagent, dialkylzinc or trialkylaluminium compounds), a diene-iridium catalyst (with arylboroxines), or a bisphosphine-cobalt catalyst (with monosilyl-acetylenes). 1,6-Conjugate additions are otherwise limited to substrates where there is full substitution at the C4 position. It is unclear why certain catalysts favour bond formation at C6, and—although there are a small number of catalytic enantioselective conjugate allyl additions—related 1,6-additions and processes involving a propargyl unit are non-existent. Here we show that an easily accessible organocopper catalyst can promote 1,6-conjugate additions of propargyl and 2-boryl-substituted allyl groups to acyclic dienoates with high selectivity. A commercially available allenyl-boron compound or a monosubstituted allene may be used. Products can be obtained in up to 83 per cent yield, >98:2 diastereomeric ratio (for allyl additions) and 99:1 enantiomeric ratio. We elucidate the mechanistic details, including the origins of high site selectivity (1,6- versus 1,4-) and enantioselectivity as a function of the catalyst

  19. Additivity of Feature-Based and Symmetry-Based Grouping Effects in Multiple Object Tracking.

    PubMed

    Wang, Chundi; Zhang, Xuemin; Li, Yongna; Lyu, Chuang

    2016-01-01

    Multiple object tracking (MOT) is an attentional process wherein people track several moving targets among several distractors. Symmetry, an important indicator of regularity, is a general spatial pattern observed in natural and artificial scenes. According to the "laws of perceptual organization" proposed by Gestalt psychologists, regularity is a principle of perceptual grouping, such as similarity and closure. A great deal of research reported that feature-based similarity grouping (e.g., grouping based on color, size, or shape) among targets in MOT tasks can improve tracking performance. However, no additive feature-based grouping effects have been reported where the tracking objects had two or more features. "Additive effect" refers to a greater grouping effect produced by grouping based on multiple cues instead of one cue. Can spatial symmetry produce a similar grouping effect similar to that of feature similarity in MOT tasks? Are the grouping effects based on symmetry and feature similarity additive? This study includes four experiments to address these questions. The results of Experiments 1 and 2 demonstrated the automatic symmetry-based grouping effects. More importantly, an additive grouping effect of symmetry and feature similarity was observed in Experiments 3 and 4. Our findings indicate that symmetry can produce an enhanced grouping effect in MOT and facilitate the grouping effect based on color or shape similarity. The "where" and "what" pathways might have played an important role in the additive grouping effect.

  20. Additivity of Feature-Based and Symmetry-Based Grouping Effects in Multiple Object Tracking

    PubMed Central

    Wang, Chundi; Zhang, Xuemin; Li, Yongna; Lyu, Chuang

    2016-01-01

    Multiple object tracking (MOT) is an attentional process wherein people track several moving targets among several distractors. Symmetry, an important indicator of regularity, is a general spatial pattern observed in natural and artificial scenes. According to the “laws of perceptual organization” proposed by Gestalt psychologists, regularity is a principle of perceptual grouping, such as similarity and closure. A great deal of research reported that feature-based similarity grouping (e.g., grouping based on color, size, or shape) among targets in MOT tasks can improve tracking performance. However, no additive feature-based grouping effects have been reported where the tracking objects had two or more features. “Additive effect” refers to a greater grouping effect produced by grouping based on multiple cues instead of one cue. Can spatial symmetry produce a similar grouping effect similar to that of feature similarity in MOT tasks? Are the grouping effects based on symmetry and feature similarity additive? This study includes four experiments to address these questions. The results of Experiments 1 and 2 demonstrated the automatic symmetry-based grouping effects. More importantly, an additive grouping effect of symmetry and feature similarity was observed in Experiments 3 and 4. Our findings indicate that symmetry can produce an enhanced grouping effect in MOT and facilitate the grouping effect based on color or shape similarity. The “where” and “what” pathways might have played an important role in the additive grouping effect. PMID:27199875

  1. Single or functionalized fullerenes interacting with heme group

    SciTech Connect

    Costa, Wallison Chaves; Diniz, Eduardo Moraes

    2014-09-15

    The heme group is responsible for iron transportation through the bloodstream, where iron participates in redox reactions, electron transfer, gases detection etc. The efficiency of such processes can be reduced if the whole heme molecule or even the iron is somehow altered from its original oxidation state, which can be caused by interactions with nanoparticles as fullerenes. To verify how such particles alter the geometry and electronic structure of heme molecule, here we report first principles calculations based on density functional theory of heme group interacting with single C{sub 60} fullerene or with C{sub 60} functionalized with small functional groups (−CH{sub 3}, −COOH, −NH{sub 2}, −OH). The calculations shown that the system heme + nanoparticle has a different spin state in comparison with heme group if the fullerene is functionalized. Also a functional group can provide a stronger binding between nanoparticle and heme molecule or inhibit the chemical bonding in comparison with single fullerene results. In addition heme molecule loses electrons to the nanoparticles and some systems exhibited a geometry distortion in heme group, depending on the binding energy. Furthermore, one find that such nanoparticles induce a formation of spin up states in heme group. Moreover, there exist modifications in density of states near the Fermi energy. Although of such changes in heme electronic structure and geometry, the iron atom remains in the heme group with the same oxidation state, so that processes that involve the iron might not be affected, only those that depend on the whole heme molecule.

  2. Additive Functions in Boolean Models of Gene Regulatory Network Modules

    PubMed Central

    Darabos, Christian; Di Cunto, Ferdinando; Tomassini, Marco; Moore, Jason H.; Provero, Paolo; Giacobini, Mario

    2011-01-01

    Gene-on-gene regulations are key components of every living organism. Dynamical abstract models of genetic regulatory networks help explain the genome's evolvability and robustness. These properties can be attributed to the structural topology of the graph formed by genes, as vertices, and regulatory interactions, as edges. Moreover, the actual gene interaction of each gene is believed to play a key role in the stability of the structure. With advances in biology, some effort was deployed to develop update functions in Boolean models that include recent knowledge. We combine real-life gene interaction networks with novel update functions in a Boolean model. We use two sub-networks of biological organisms, the yeast cell-cycle and the mouse embryonic stem cell, as topological support for our system. On these structures, we substitute the original random update functions by a novel threshold-based dynamic function in which the promoting and repressing effect of each interaction is considered. We use a third real-life regulatory network, along with its inferred Boolean update functions to validate the proposed update function. Results of this validation hint to increased biological plausibility of the threshold-based function. To investigate the dynamical behavior of this new model, we visualized the phase transition between order and chaos into the critical regime using Derrida plots. We complement the qualitative nature of Derrida plots with an alternative measure, the criticality distance, that also allows to discriminate between regimes in a quantitative way. Simulation on both real-life genetic regulatory networks show that there exists a set of parameters that allows the systems to operate in the critical region. This new model includes experimentally derived biological information and recent discoveries, which makes it potentially useful to guide experimental research. The update function confers additional realism to the model, while reducing the complexity

  3. Additive functions in boolean models of gene regulatory network modules.

    PubMed

    Darabos, Christian; Di Cunto, Ferdinando; Tomassini, Marco; Moore, Jason H; Provero, Paolo; Giacobini, Mario

    2011-01-01

    Gene-on-gene regulations are key components of every living organism. Dynamical abstract models of genetic regulatory networks help explain the genome's evolvability and robustness. These properties can be attributed to the structural topology of the graph formed by genes, as vertices, and regulatory interactions, as edges. Moreover, the actual gene interaction of each gene is believed to play a key role in the stability of the structure. With advances in biology, some effort was deployed to develop update functions in boolean models that include recent knowledge. We combine real-life gene interaction networks with novel update functions in a boolean model. We use two sub-networks of biological organisms, the yeast cell-cycle and the mouse embryonic stem cell, as topological support for our system. On these structures, we substitute the original random update functions by a novel threshold-based dynamic function in which the promoting and repressing effect of each interaction is considered. We use a third real-life regulatory network, along with its inferred boolean update functions to validate the proposed update function. Results of this validation hint to increased biological plausibility of the threshold-based function. To investigate the dynamical behavior of this new model, we visualized the phase transition between order and chaos into the critical regime using Derrida plots. We complement the qualitative nature of Derrida plots with an alternative measure, the criticality distance, that also allows to discriminate between regimes in a quantitative way. Simulation on both real-life genetic regulatory networks show that there exists a set of parameters that allows the systems to operate in the critical region. This new model includes experimentally derived biological information and recent discoveries, which makes it potentially useful to guide experimental research. The update function confers additional realism to the model, while reducing the complexity

  4. Development of additional tasks for the executive function performance test.

    PubMed

    Hahn, Bridget; Baum, Carolyn; Moore, Jennifer; Ehrlich-Jones, Linda; Spoeri, Susan; Doherty, Meghan; Wolf, Timothy J

    2014-01-01

    OBJECTIVE. The Executive Function Performance Test (EFPT) is a reliable and valid performance-based assessment of executive function for people with stroke. The objective of this study was to enhance the clinical utility of the EFPT by developing and testing additional tasks for the EFPT in the Alternate EFPT (aEFPT). METHOD. We performed a cross-sectional study with poststroke participants (n = 25) and healthy control participants (n = 25). All participants completed a neuropsychological assessment battery and both the EFPT and the aEFPT. RESULTS. No statistically significant differences were found between the EFPT and the aEFPT when examining total scores, construct scores, and two overall task scores. Correlations between the aEFPT and the neuropsychological measures were adequate to strong (r2s = .59-.83). CONCLUSION. The aEFPT tasks are comparable to the original EFPT tasks, providing occupational therapy practitioners with additional tasks that can be used clinically to identify performance-based executive function deficits in people with stroke.

  5. Functionalized 3D Architected Materials via Thiol-Michael Addition and Two-Photon Lithography.

    PubMed

    Yee, Daryl W; Schulz, Michael D; Grubbs, Robert H; Greer, Julia R

    2017-02-20

    Fabrication of functionalized 3D architected materials is achieved by a facile method using functionalized acrylates synthesized via thiol-Michael addition, which are then polymerized using two-photon lithography. A wide variety of functional groups can be attached, from Boc-protected amines to fluoroalkanes. Modification of surface wetting properties and conjugation with fluorescent tags are demonstrated to highlight the potential applications of this technique.

  6. Fuzzy Number Addition with the Application of Horizontal Membership Functions

    PubMed Central

    Piegat, Andrzej; Pluciński, Marcin

    2015-01-01

    The paper presents addition of fuzzy numbers realised with the application of the multidimensional RDM arithmetic and horizontal membership functions (MFs). Fuzzy arithmetic (FA) is a very difficult task because operations should be performed here on multidimensional information granules. Instead, a lot of FA methods use α-cuts in connection with 1-dimensional classical interval arithmetic that operates not on multidimensional granules but on 1-dimensional intervals. Such approach causes difficulties in calculations and is a reason for arithmetical paradoxes. The multidimensional approach allows for removing drawbacks and weaknesses of FA. It is possible thanks to the application of horizontal membership functions which considerably facilitate calculations because now uncertain values can be inserted directly into equations without using the extension principle. The paper shows how the addition operation can be realised on independent fuzzy numbers and on partly or fully dependent fuzzy numbers with taking into account the order relation and how to solve equations, which can be a difficult task for 1-dimensional FAs. PMID:26199953

  7. Functional gene group analysis identifies synaptic gene groups as risk factor for schizophrenia

    PubMed Central

    Lips, E S; Cornelisse, L N; Toonen, R F; Min, J L; Hultman, C M; Holmans, P A; O'Donovan, M C; Purcell, S M; Smit, A B; Verhage, M; Sullivan, P F; Visscher, P M; Posthuma, D

    2012-01-01

    Schizophrenia is a highly heritable disorder with a polygenic pattern of inheritance and a population prevalence of ∼1%. Previous studies have implicated synaptic dysfunction in schizophrenia. We tested the accumulated association of genetic variants in expert-curated synaptic gene groups with schizophrenia in 4673 cases and 4965 healthy controls, using functional gene group analysis. Identifying groups of genes with similar cellular function rather than genes in isolation may have clinical implications for finding additional drug targets. We found that a group of 1026 synaptic genes was significantly associated with the risk of schizophrenia (P=7.6 × 10−11) and more strongly associated than 100 randomly drawn, matched control groups of genetic variants (P<0.01). Subsequent analysis of synaptic subgroups suggested that the strongest association signals are derived from three synaptic gene groups: intracellular signal transduction (P=2.0 × 10−4), excitability (P=9.0 × 10−4) and cell adhesion and trans-synaptic signaling (P=2.4 × 10−3). These results are consistent with a role of synaptic dysfunction in schizophrenia and imply that impaired intracellular signal transduction in synapses, synaptic excitability and cell adhesion and trans-synaptic signaling play a role in the pathology of schizophrenia. PMID:21931320

  8. Functional gene group analysis identifies synaptic gene groups as risk factor for schizophrenia.

    PubMed

    Lips, E S; Cornelisse, L N; Toonen, R F; Min, J L; Hultman, C M; Holmans, P A; O'Donovan, M C; Purcell, S M; Smit, A B; Verhage, M; Sullivan, P F; Visscher, P M; Posthuma, D

    2012-10-01

    Schizophrenia is a highly heritable disorder with a polygenic pattern of inheritance and a population prevalence of ~1%. Previous studies have implicated synaptic dysfunction in schizophrenia. We tested the accumulated association of genetic variants in expert-curated synaptic gene groups with schizophrenia in 4673 cases and 4965 healthy controls, using functional gene group analysis. Identifying groups of genes with similar cellular function rather than genes in isolation may have clinical implications for finding additional drug targets. We found that a group of 1026 synaptic genes was significantly associated with the risk of schizophrenia (P=7.6 × 10(-11)) and more strongly associated than 100 randomly drawn, matched control groups of genetic variants (P<0.01). Subsequent analysis of synaptic subgroups suggested that the strongest association signals are derived from three synaptic gene groups: intracellular signal transduction (P=2.0 × 10(-4)), excitability (P=9.0 × 10(-4)) and cell adhesion and trans-synaptic signaling (P=2.4 × 10(-3)). These results are consistent with a role of synaptic dysfunction in schizophrenia and imply that impaired intracellular signal transduction in synapses, synaptic excitability and cell adhesion and trans-synaptic signaling play a role in the pathology of schizophrenia.

  9. Functional group diversity increases with modularity in complex food webs

    PubMed Central

    Montoya, D.; Yallop, M.L.; Memmott, J.

    2015-01-01

    Biodiversity increases the ability of ecosystems to provide multiple functions. Most studies report a positive relationship between species richness and the number of ecosystem functions. However, it is not known whether the number of functional groups is related to the structure of the underlying species interaction network. Here we present food web data from 115 salt marsh islands and show that network structure is associated with the number of functional groups present. Functional group diversity is heterogeneously distributed across spatial scales, with some islands hosting more functional groups than others. Functional groups form modules within the community so that food webs with more modular architectures have more functional group diversity. Further, in communities with different interaction types, modularity can be seen as the multifunctional equivalent of trophic complementarity. Collectively, these findings reveal spatial heterogeneity in the number of functional groups that emerges from patterns in the structure of the food web. PMID:26059871

  10. Functional group diversity increases with modularity in complex food webs.

    PubMed

    Montoya, D; Yallop, M L; Memmott, J

    2015-06-10

    Biodiversity increases the ability of ecosystems to provide multiple functions. Most studies report a positive relationship between species richness and the number of ecosystem functions. However, it is not known whether the number of functional groups is related to the structure of the underlying species interaction network. Here we present food web data from 115 salt marsh islands and show that network structure is associated with the number of functional groups present. Functional group diversity is heterogeneously distributed across spatial scales, with some islands hosting more functional groups than others. Functional groups form modules within the community so that food webs with more modular architectures have more functional group diversity. Further, in communities with different interaction types, modularity can be seen as the multifunctional equivalent of trophic complementarity. Collectively, these findings reveal spatial heterogeneity in the number of functional groups that emerges from patterns in the structure of the food web.

  11. Controlling Functional Group Architecture in Artificial Cells

    DTIC Science & Technology

    2015-07-02

    cycloadditions to modify reactive groups within the phospholipid membrane structure and how the nature of the reactive elements, the copper catalyst ...within the phospholipid membrane structure and how the nature of the reactive elements, the copper catalyst , the azide, and the alkyne, affect the...the copper catalyst , the azide, and the alkyne, affect the location and yield of the resulting product in the phospholipid membrane. 2. Reasons why

  12. Testing for Additivity at Select Mixture Groups of Interest Based on Statistical Equivalence Testing Methods

    SciTech Connect

    Stork, LeAnna M.; Gennings, Chris; Carchman, Richard; Carter, Jr., Walter H.; Pounds, Joel G.; Mumtaz, Moiz

    2006-12-01

    Several assumptions, defined and undefined, are used in the toxicity assessment of chemical mixtures. In scientific practice mixture components in the low-dose region, particularly subthreshold doses, are often assumed to behave additively (i.e., zero interaction) based on heuristic arguments. This assumption has important implications in the practice of risk assessment, but has not been experimentally tested. We have developed methodology to test for additivity in the sense of Berenbaum (Advances in Cancer Research, 1981), based on the statistical equivalence testing literature where the null hypothesis of interaction is rejected for the alternative hypothesis of additivity when data support the claim. The implication of this approach is that conclusions of additivity are made with a false positive rate controlled by the experimenter. The claim of additivity is based on prespecified additivity margins, which are chosen using expert biological judgment such that small deviations from additivity, which are not considered to be biologically important, are not statistically significant. This approach is in contrast to the usual hypothesis-testing framework that assumes additivity in the null hypothesis and rejects when there is significant evidence of interaction. In this scenario, failure to reject may be due to lack of statistical power making the claim of additivity problematic. The proposed method is illustrated in a mixture of five organophosphorus pesticides that were experimentally evaluated alone and at relevant mixing ratios. Motor activity was assessed in adult male rats following acute exposure. Four low-dose mixture groups were evaluated. Evidence of additivity is found in three of the four low-dose mixture groups.The proposed method tests for additivity of the whole mixture and does not take into account subset interactions (e.g., synergistic, antagonistic) that may have occurred and cancelled each other out.

  13. Pd(II)-Catalyzed C–H Functionalizations Directed by Distal Weakly Coordinating Functional Groups

    PubMed Central

    Li, Gang; Wan, Li; Zhang, Guofu; Leow, Dasheng; Spangler, Jillian

    2015-01-01

    Ortho-C(sp2)–H olefination and acetoxylation of broadly useful synthetic building blocks phenylacetyl Weinreb amides, esters, and ketones are developed without installing an additional directing group. The interplay between the distal weak coordination and the ligand-acceleration is crucial for these reactions to proceed under mild conditions. The tolerance of longer distance between the target C–H bonds and the directing functional groups also allows for the functionalizations of more distal C–H bonds in hydrocinnamoyl ketones, Weinreb amides and biphenyl Weinreb amides. Mechanistically, the coordination of these carbonyl groups and the bisdentate amino acid ligand with Pd(II) centers provides further evidence for our early hypothesis that the carbonyl groups of the potassium carboxylate is responsible for the directed C–H activation of carboxylic acids. PMID:25768039

  14. Preparation for Group Therapy: The Effects of Preparer and Modality on Group Process and Individual Functioning.

    ERIC Educational Resources Information Center

    Bowman, Vicki E.; DeLucia, Janice L.

    1993-01-01

    Examined effects of preparer (leader versus other personnel) and modality (group versus individual) on expectations about therapy, anxiety, group and individual functioning, and leader functioning in group therapy preparation program. Findings from 32 graduate students revealed that preparation can have positive effect on clients' beliefs,…

  15. Addition of lysophospholipids with large head groups to cells inhibits Shiga toxin binding

    PubMed Central

    Ailte, Ieva; Lingelem, Anne Berit Dyve; Kavaliauskiene, Simona; Bergan, Jonas; Kvalvaag, Audun Sverre; Myrann, Anne-Grethe; Skotland, Tore; Sandvig, Kirsten

    2016-01-01

    Shiga toxin (Stx), an AB5 toxin, binds specifically to the neutral glycosphingolipid Gb3 at the cell surface before being transported into cells. We here demonstrate that addition of conical lysophospholipids (LPLs) with large head groups inhibit Stx binding to cells whereas LPLs with small head groups do not. Lysophosphatidylinositol (LPI 18:0), the most efficient LPL with the largest head group, was selected for in-depth investigations to study how the binding of Stx is regulated. We show that the inhibition of Stx binding by LPI is reversible and possibly regulated by cholesterol since addition of methyl-β-cyclodextrin (mβCD) reversed the ability of LPI to inhibit binding. LPI-induced inhibition of Stx binding is independent of signalling and membrane turnover as it occurs in fixed cells as well as after depletion of cellular ATP. Furthermore, data obtained with fluorescent membrane dyes suggest that LPI treatment has a direct effect on plasma membrane lipid packing with shift towards a liquid disordered phase in the outer leaflet, while lysophosphoethanolamine (LPE), which has a small head group, does not. In conclusion, our data show that cellular treatment with conical LPLs with large head groups changes intrinsic properties of the plasma membrane and modulates Stx binding to Gb3. PMID:27458147

  16. Functions of Propolis as a natural feed additive in poultry

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Propolis is a resinous hive product collected by honeybees from various sources of plants. Numerous scientific investigations have been focused on the biological activities of propolis and its functions as a health supplement in humans. It could have similar function in other animals, such as poultr...

  17. [Functional feeding groups of macroinvertebrates in Gaira river, Colombia].

    PubMed

    Rodríguez-Barrios, Javier; Ospina-Tórres, Rodulfo; Turizo-Correa, Rodrigo

    2011-12-01

    Tropical rivers are frequently described on their biodiversity but few studies have considered the ecological value of this richness in their food webs. We determined the trophic structure of aquatic macroinvertebrate communities (expressed in the richness and abundance of taxa and biomass proportions of different functional feeding groups) at the level of the river, stretch and microhabitats (functional units - UFs). We evaluated the spatial and temporal variation of these descriptors during wet and dry events, and selected three sites associated with different altitudinal belts. We reported 109 taxa, with 11167 individuals who contributed 107.11g of biomass. Density of macroinvertebrates was favored with increasing height, and biomass showed the opposite pattern (K-W = 10.1, d.f. = 1, p < 0.05), due to the addition of large crustaceans (Macrobrachium), and the taxa diversity was higher in the middle stretch of the river (H'=3.16). The Gaira stream runs through a mid-sized river basin, for this reason we found mainly bedrock (epilithon = 50.5%), gravel and sand (43.7%). The functional unit with more habitat and food resources that contains a higher abundance of leaf litter macroinvertebrates was foliage followed by epilithon, fine sediment and gravel-sand (K-W = 25.3, d.f. = 3, p < 0.05). The biomass values of these organisms were higher in leaves followed by gravel-sands, epilithon and sediment (K-W = 15.3, d.f. = 3, p < 0.05). Autochthonous biomass input by different functional feeding groups can be considered very low, but they define the functionality of the stream, being represented almost exclusively by shredders (Macrobrachium, 73%), present only in the lower reaches, followed by shredder Leptonema with 15%, located mostly in the upper reaches and predatory stoneflies of the genus Anacroneuria to 6.56%, which dominated in the middle stretch of stream. Excluding Macrobrachium from the analysis, there was dominance of Anacroneuria in the lower reaches

  18. Development of an efficient amine-functionalized glass platform by additional silanization treatment with alkylsilane.

    PubMed

    Kamisetty, Nagendra Kumar; Pack, Seung Pil; Nonogawa, Mitsuru; Devarayapalli, Kamakshaiah Charyulu; Kodaki, Tsutomu; Makino, Keisuke

    2006-11-01

    Aminosilane-treated molecular layers on glass surfaces are frequently used as functional platforms for biosensor preparation. All the amino groups present on the surface are not available in reactive forms, because surface amino groups interact with remaining unreacted surface silanol groups. Such nonspecific interactions might reduce the efficiency of chemical immobilization of biomolecules such as DNA, enzymes, antibodies, etc., in biosensor fabrication. To improve immobilization efficiency we have used additional surface silanization with alkylsilane (capping) to convert the remaining silanol groups into Si-O-Si linkages, thereby liberating the amino groups from nonspecific interaction with the silanol groups. We prepared different types of capped amine surface and evaluated the effect of capping on immobilization efficiency by investigating the fluorescence intensity of Cy3-NHS (N-hydroxysuccinimide) dye that reacted with amino groups. The results indicate that most of the capped amine surfaces resulted in enhanced efficiency of immobilization of Cy3-NHS compared with the untreated control amine surface. We found a trend that trialkoxysilanes had greater capping effects on immobilization efficiency than monoalkoxysilanes. It was also found that the aliphatic chain of alkylsilane, which does not participate in the capping of the silanol, had an important function in enhancing immobilization efficiency. These results would be useful for preparation of an amine-modified surface platform, with enhanced immobilization efficiency, which is essential for developing many kinds of biosensors on a silica matrix.

  19. Functional Group Analysis of Biomass Burning Particles Using Infrared Spectroscopy

    NASA Astrophysics Data System (ADS)

    Horrell, K.; Lau, A.; Bond, T.; Iraci, L. T.

    2008-12-01

    Biomass burning is a significant source of particulate organic carbon in the atmosphere. These particles affect the energy balance of the atmosphere directly by absorbing and scattering solar radiation, and indirectly through their ability to act as cloud condensation nuclei (CCN). The chemical composition of biomass burning particles influences their ability to act as CCN, thus understanding the chemistry of these particles is required for understanding their effects on climate and air quality. As climate change influences the frequency and severity of boreal forest fires, the influence of biomass burning aerosols on the atmosphere may become significantly greater. Only a small portion of the organic carbon (OC) fraction of these particles has been identified at the molecular level, although several studies have explored the general chemical classes found in biomass burning smoke. To complement those studies and provide additional information about the reactive functional groups present, we are developing a method for polarity-based separation of compound classes found in the OC fraction, followed by infrared (IR) spectroscopic analysis of each polarity fraction. It is our goal to find a simple, relatively low-tech method which will provide a moderate chemical understanding of the entire suite of compounds present in the OC fraction of biomass burning particles. Here we present preliminary results from pine and oak samples representative of Midwestern United States forests burned at several different temperatures. Wood type and combustion temperature are both seen to affect the composition of the particles. The latter seems to affect relative contributions of certain functional groups, while oak demonstrates at least one additional chemical class of compounds, particularly at lower burning temperatures, where gradual solid-gas phase reactions can produce relatively large amounts of incompletely oxidized products.

  20. Additional applications of the Lambert W function in physics

    NASA Astrophysics Data System (ADS)

    Houari, Ahmed

    2013-05-01

    In this paper, using the Lambert W function, I derive closed-form analytical expressions for the decay constant of an exponentially decaying process and the time constant of a process subject to a linear resistive force. Similarly, I derive closed-form analytical formulae for the electrical resistivity of a metal and the temperature of a thermionic emitter material. Besides their theoretical importance, the results obtained will be of interest to teachers involved in undergraduate physics experiments.

  1. Phosphazene additives

    DOEpatents

    Harrup, Mason K; Rollins, Harry W

    2013-11-26

    An additive comprising a phosphazene compound that has at least two reactive functional groups and at least one capping functional group bonded to phosphorus atoms of the phosphazene compound. One of the at least two reactive functional groups is configured to react with cellulose and the other of the at least two reactive functional groups is configured to react with a resin, such as an amine resin of a polycarboxylic acid resin. The at least one capping functional group is selected from the group consisting of a short chain ether group, an alkoxy group, or an aryloxy group. Also disclosed are an additive-resin admixture, a method of treating a wood product, and a wood product.

  2. Functional Analytic Psychotherapy for Interpersonal Process Groups: A Behavioral Application

    ERIC Educational Resources Information Center

    Hoekstra, Renee

    2008-01-01

    This paper is an adaptation of Kohlenberg and Tsai's work, Functional Analytical Psychotherapy (1991), or FAP, to group psychotherapy. This author applied a behavioral rationale for interpersonal process groups by illustrating key points with a hypothetical client. Suggestions are also provided for starting groups, identifying goals, educating…

  3. Differential Item Functioning Detection across Two Methods of Defining Group Comparisons: Pairwise and Composite Group Comparisons

    ERIC Educational Resources Information Center

    Sari, Halil Ibrahim; Huggins, Anne Corinne

    2015-01-01

    This study compares two methods of defining groups for the detection of differential item functioning (DIF): (a) pairwise comparisons and (b) composite group comparisons. We aim to emphasize and empirically support the notion that the choice of pairwise versus composite group definitions in DIF is a reflection of how one defines fairness in DIF…

  4. Additive Manufacturing of Functional Elements on Sheet Metal

    NASA Astrophysics Data System (ADS)

    Schaub, Adam; Ahuja, Bhrigu; Butzhammer, Lorenz; Osterziel, Johannes; Schmidt, Michael; Merklein, Marion

    Laser Beam Melting (LBM) process with its advantages of high design flexibility and free form manufacturing methodology is often applied limitedly due to its low productivity and unsuitability for mass production compared to conventional manufacturing processes. In order to overcome these limitations, a hybrid manufacturing methodology is developed combining the additive manufacturing process of laser beam melting with sheet forming processes. With an interest towards aerospace and medical industry, the material in focus is Ti-6Al-4V. Although Ti-6Al-4V is a commercially established material and its application for LBM process has been extensively investigated, the combination of LBM of Ti-6Al-4V with sheet metal still needs to be researched. Process dynamics such as high temperature gradients and thermally induced stresses lead to complex stress states at the interaction zone between the sheet and LBM structure. Within the presented paper mechanical characterization of hybrid parts will be performed by shear testing. The association of shear strength with process parameters is further investigated by analyzing the internal structure of the hybrid geometry at varying energy inputs during the LBM process. In order to compare the hybrid manufacturing methodology with conventional fabrication, the conventional methodologies subtractive machining and state of the art Laser Beam Melting is evaluated within this work. These processes will be analyzed for their mechanical characteristics and productivity by determining the build time and raw material consumption for each case. The paper is concluded by presenting the characteristics of the hybrid manufacturing methodology compared to alternative manufacturing technologies.

  5. Quantitative evaluation of interaction force between functional groups in protein and polymer brush surfaces.

    PubMed

    Sakata, Sho; Inoue, Yuuki; Ishihara, Kazuhiko

    2014-03-18

    To understand interactions between polymer surfaces and different functional groups in proteins, interaction forces were quantitatively evaluated by force-versus-distance curve measurements using atomic force microscopy with a functional-group-functionalized cantilever. Various polymer brush surfaces were systematically prepared by surface-initiated atom transfer radical polymerization as well-defined model surfaces to understand protein adsorption behavior. The polymer brush layers consisted of phosphorylcholine groups (zwitterionic/hydrophilic), trimethylammonium groups (cationic/hydrophilic), sulfonate groups (anionic/hydrophilic), hydroxyl groups (nonionic/hydrophilic), and n-butyl groups (nonionic/hydrophobic) in their side chains. The interaction forces between these polymer brush surfaces and different functional groups (carboxyl groups, amino groups, and methyl groups, which are typical functional groups existing in proteins) were quantitatively evaluated by force-versus-distance curve measurements using atomic force microscopy with a functional-group-functionalized cantilever. Furthermore, the amount of adsorbed protein on the polymer brush surfaces was quantified by surface plasmon resonance using albumin with a negative net charge and lysozyme with a positive net charge under physiological conditions. The amount of proteins adsorbed on the polymer brush surfaces corresponded to the interaction forces generated between the functional groups on the cantilever and the polymer brush surfaces. The weakest interaction force and least amount of protein adsorbed were observed in the case of the polymer brush surface with phosphorylcholine groups in the side chain. On the other hand, positive and negative surfaces generated strong forces against the oppositely charged functional groups. In addition, they showed significant adsorption with albumin and lysozyme, respectively. These results indicated that the interaction force at the functional group level might be

  6. Mutations in RIT1 cause Noonan syndrome – additional functional evidence and expanding the clinical phenotype

    PubMed Central

    Koenighofer, Martin; Hung, Christina Y.; McCauley, Jacob L.; Dallman, Julia; Back, Emma J.; Mihalek, Ivana; Gripp, Karen W.; Sol-Church, Katia; Rusconi, Paolo; Zhang, Zhaiyi; Shi, Geng-Xian; Andres, Douglas A.; Bodamer, Olaf A.

    2015-01-01

    RASopathies are a clinically heterogeneous group of conditions caused by mutations in one of sixteen proteins in the RAS-MAPK pathway. Recently, mutations in RIT1 were identified as a novel cause for Noonan syndrome. Here we provide additional functional evidence for a causal role of RIT1 mutations and expand the associated phenotypic spectrum. We identified two de novo missense variants p.Met90Ile and, p.Ala57Gly. Both variants resulted in increased MEK-ERK signaling compared to wild-type, underscoring gain-of-function as the primary functional mechanism. Introduction of p.Met90Ile and p.Ala57Gly into zebrafish embryos reproduced not only aspects of the human phenotype but also revealed abnormalities of eye development, emphasizing the importance of RIT1 for spatial and temporal organization of the growing organism. In addition, we observed severe lymphedema of the lower extremity and genitalia in one patient. We provide additional evidence for a causal relationship between pathogenic mutations in RIT1, increased RAS-MAPK/MEK-ERK signaling and the clinical phenotype. The mutant RIT1 protein may possess reduced GTPase activity or a diminished ability to interact with cellular GTPase activating proteins, however the precise mechanism remains unknown. The phenotypic spectrum is likely to expand and includes lymphedema of the lower extremities in addition to nuchal hygroma. PMID:25959749

  7. Selectivity in the Addition Reactions of Organometallic Reagents to Aziridine-2-carboxaldehydes: The Effects of Protecting Groups and Substitution Patterns

    PubMed Central

    Kulshrestha, Aman; Schomaker, Jennifer M.; Holmes, Daniel; Staples, Richard J.; Jackson, James E.; Borhan, Babak

    2014-01-01

    Good to excellent stereo-selectivity has been found in the addition reactions of Grignard and organo-zinc reagents to N-protected aziridine-2-carboxaldehydes. Specifically, high syn selectivity was obtained with benzyl-protected cis, tert-butyloxycar-bonyl-protected trans, and tosyl-pro-tected 2,3-disubstituted aziridine-2-car-boxaldehydes. Furthermore, rate and selectivity effects of ring substituents, temperature, solvent, and Lewis acid and base modifiers were studied. The diastereomeric preference of addition is dominated by the substrate aziri-dines’ substitution pattern and especially the electronic character and conformational preferences of the nitrogen protecting groups. To help rationalize the observed stereochemical outcomes, conformational and electronic structural analyses of a series of model systems representing the various substitution patterns have been explored by density functional calculations at the B3LYP/6–31G* level of theory with the SM8 solvation model to account for solvent effects. PMID:21928447

  8. ProPhenol-Catalyzed Asymmetric Additions by Spontaneously Assembled Dinuclear Main Group Metal Complexes

    PubMed Central

    2016-01-01

    Conspectus The development of catalytic enantioselective transformations has been the focus of many research groups over the past half century and is of paramount importance to the pharmaceutical and agrochemical industries. Since the award of the Nobel Prize in 2001, the field of enantioselective transition metal catalysis has soared to new heights, with the development of more efficient catalysts and new catalytic transformations at increasing frequency. Furthermore, catalytic reactions that allow higher levels of redox- and step-economy are being developed. Thus, alternatives to asymmetric alkene dihydroxylation and the enantioselective reduction of α,β-unsaturated ketones can invoke more strategic C–C bond forming reactions, such as asymmetric aldol reactions of an aldehyde with α-hydroxyketone donors or enantioselective alkynylation of an aldehyde, respectively. To facilitate catalytic enantioselective addition reactions, including the aforementioned aldol and alkynylation reactions, our lab has developed the ProPhenol ligand. In this Account, we describe the development and application of the ProPhenol ligand for asymmetric additions of both carbon- and heteroatom-based nucleophiles to various electrophiles. The ProPhenol ligand spontaneously forms chiral dinuclear metal complexes when treated with an alkyl metal reagent, such as Et2Zn or Bu2Mg. The resulting complex contains both a Lewis acidic site to activate an electrophile and a Brønsted basic site to deprotonate a pronucleophile. Initially, our research focused on the use of Zn-ProPhenol complexes to facilitate the direct aldol reaction. Fine tuning of the reaction through ligand modification and the use of additives enabled the direct aldol reaction to proceed in high yields and stereoselectivities with a broad range of donor substrates, including acetophenones, methyl ynones, methyl vinyl ketone, acetone, α-hydroxy carbonyl compounds, and glycine Schiff bases. Additionally, an analogous

  9. Functional Grouping in Residential Homes for People with Intellectual Disabilities.

    ERIC Educational Resources Information Center

    Mansell, Jim; Beadle-Brown, Julie; Macdonald, Susan; Ashman, Bev

    2003-01-01

    The effects of functional grouping of 303 people with intellectual disabilities on care practices in English group homes were investigated. Residents who were non-ambulant were rated as receiving care with less interpersonal warmth and residents with severe challenging behavior were rated as receiving care with less interpersonal warmth and…

  10. Multipole model for the electron group functions method.

    PubMed

    Tchougréeff, A L; Tokmachev, A M; Dronskowski, R

    2009-10-22

    Electron groups provide a natural way to introduce local concepts into quantum chemistry, and the wave functions based on the group products can be considered as a framework for constructing efficient computational methods in terms of "observable" parts of molecular systems. The elements of the group wave functions (electronic structure variables) can be optimized by requiring the number of operations proportional to the size of the molecule. This directly leads to computational methods linearly scaling for large molecular systems. In the present work we consider a particular case of such a wave function implemented for the semiempirical NDDO Hamiltonian. The electron groups are expressed in terms of optimized atomic (hybrid) orbitals with chemical bonds described by geminals and the delocalized groups described by Slater determinants (with or without spin restriction). This scheme is very fast by itself but its speed is considerably limited by the computations of the interatomic Coulomb interactions. Here we develop a consistent method based on group functions which uses the multipole scheme for interatomic interactions. The explicit usage of the atomic multipoles makes the method extremely fast, although the numerical efficiency is largely achieved due to the local character of the electron groups involved. We discuss numerical characteristics of the new method as well as its possible parametrization. We apply this method to study dodecahedral water clusters with hydrogen fluoride substitution and base the analysis on the exhaustive calculation of all symmetry-independent hydrogen-bond networks.

  11. Optical behaviour of functional groups of graphene oxide

    NASA Astrophysics Data System (ADS)

    Narayanam, Pavan K.; Sankaran, K.

    2016-10-01

    Optical properties of graphene oxide (GO) dispersed in aqueous medium with aging and pH variations were investigated along with concurrent changes of oxygen functional groups of GO. Freshly prepared GO exhibit strong excitation wavelength dependent luminescence, which gets gradually nullified with aging due to the drastic reduction in fraction of polar hydroxyl groups. Fourier transform infrared studies indicated that functional groups of GO undergo spontaneous modification with aging in aqueous medium, resulting in suppression of epoxide groups and enriched adsorption of water molecules. When the pH of GO dispersed in aqueous medium was varied, unique transformations of functional groups take place causing major disruption to the sp2 hybridised carbon domains of GO. Concurrent changes in luminescence of GO infer that the broad emission from freshly prepared GO has large contribution from disorder induced localised states due to hydroxyl, epoxide, carboxyl groups and changes in relative fractions of these groups with aging and pH variations of GO dispersions strongly influence the intensity as well as emission wavelength region of GO. Especially emission features of GO are strongly influenced by the presence, fraction and transformations of epoxide and hydroxyl groups of GO.

  12. Implement the medical group revenue function. Create competitive advantage.

    PubMed

    Colucci, C

    1998-01-01

    This article shows medical groups how they can employ new financial management and information technology techniques to safeguard their revenue and income streams. These managerial techniques stem from the application of the medical group revenue function, which is defined herein. This article also describes how the medical group revenue function can be used to create value by employing a database and a decision support system. Finally, the article describes how the decision support system can be used to create competitive advantage. Through the wise use of internally generated information, medical groups can negotiate better contract terms, improve their operations, cut their costs, embark on capital investment programs and improve market share. As medical groups gain market power by improving in these areas, they will be more attractive to potential strategic allies, payers and investment bankers.

  13. Detection of rare functional variants using group ISIS.

    PubMed

    Niu, Yue S; Hao, Ning; An, Lingling

    2011-11-29

    Genome-wide association studies have been firmly established in investigations of the associations between common genetic variants and complex traits or diseases. However, a large portion of complex traits and diseases cannot be explained well by common variants. Detecting rare functional variants becomes a trend and a necessity. Because rare variants have such a small minor allele frequency (e.g., <0.05), detecting functional rare variants is challenging. Group iterative sure independence screening (ISIS), a fast group selection tool, was developed to select important genes and the single-nucleotide polymorphisms within. The performance of the group ISIS and group penalization methods is compared for detecting important genes in the Genetic Analysis Workshop 17 data. The results suggest that the group ISIS is an efficient tool to discover genes and single-nucleotide polymorphisms associated to phenotypes.

  14. Functional movement screen scores in a group of running athletes.

    PubMed

    Loudon, Janice K; Parkerson-Mitchell, Amy J; Hildebrand, Laurie D; Teague, Connie

    2014-04-01

    The purpose of this study was to determine the mean values of the functional movement screen (FMS) in a group of long-distance runners. The secondary aims were to investigate whether the FMS performance differed between sexes and between young and older runners. Forty-three runners, 16 women (mean age = 33.5 years, height = 165.2 cm, weight = 56.3 kg, and body mass index [BMI] = 20.6) and 27 men (mean age = 39.3 years, height = 177.6 cm, weight = 75.8 kg, and BMI = 24.2) performed the FMS. All the runners were injury-free and ran >30 km·wk. Independent t-tests were performed on the composite scores to examine the differences between men and women and also between young (<40 years) and older runners (>40 years). Contingency tables (2 × 2) were developed for each of the 7 screening tests to further look at the differences in groups for each single test. The χ values were calculated to determine significant differences. Statistical significance was set at p ≤ 0.05. There was no significant difference in the composite score between women and men. There were significant differences between the sexes in the push-up and straight leg test scores, with the women scoring better on each test. A significant difference was found in the composite scores between younger and older runners (p < 0.000). Additional score differences were found for the squat, hurdle step, and in-line lunge tests with the younger runners scoring better. This study provided mean values for the FMS in a cohort of long-distance runners. These values can be used as a reference for comparing FMST scores in other runners who are screened with this tool.

  15. High-performance functional Renormalization Group calculations for interacting fermions

    NASA Astrophysics Data System (ADS)

    Lichtenstein, J.; Sánchez de la Peña, D.; Rohe, D.; Di Napoli, E.; Honerkamp, C.; Maier, S. A.

    2017-04-01

    We derive a novel computational scheme for functional Renormalization Group (fRG) calculations for interacting fermions on 2D lattices. The scheme is based on the exchange parametrization fRG for the two-fermion interaction, with additional insertions of truncated partitions of unity. These insertions decouple the fermionic propagators from the exchange propagators and lead to a separation of the underlying equations. We demonstrate that this separation is numerically advantageous and may pave the way for refined, large-scale computational investigations even in the case of complex multiband systems. Furthermore, on the basis of speedup data gained from our implementation, it is shown that this new variant facilitates efficient calculations on a large number of multi-core CPUs. We apply the scheme to the t ,t‧ Hubbard model on a square lattice to analyze the convergence of the results with the bond length of the truncation of the partition of unity. In most parameter areas, a fast convergence can be observed. Finally, we compare to previous results in order to relate our approach to other fRG studies.

  16. Accessing siloxane functionalized polynorbornenes via vinyl-addition polymerization for CO2 separation membranes

    DOE PAGES

    Mahurin, Shannon Mark; Sokolov, Alexei P.; Saito, Tomonori; ...

    2016-07-06

    Here, the vinyl addition polymerization of norbornylbased monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans-[Ni(C6F5)2(SbPh3)2]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxanesubstituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability (Td ≥ 362 °C) and were cast into membranes that displayed high CO2 permeability and enhanced CO2/N2 selectivity as compared to related materials.

  17. Cinchona Alkaloid Catalyzed Sulfa-Michael Addition Reactions Leading to Enantiopure β-Functionalized Cysteines.

    PubMed

    Breman, Arjen C; Telderman, Suze E M; van Santen, Roy P M; Scott, Jamie I; van Maarseveen, Jan H; Ingemann, Steen; Hiemstra, Henk

    2015-11-06

    Sulfa-Michael additions to α,β-unsaturated N-acylated oxazolidin-2-ones and related α,β-unsaturated α-amino acid derivatives have been enantioselectively catalyzed by Cinchona alkaloids functionalized with a hydrogen bond donating group at the C6' position. The series of Cinchona alkaloids includes known C6' (thio)urea and sulfonamide derivatives and several novel species with a benzimidazole, squaramide or a benzamide group at the C6' position. The sulfonamides were especially suited as bifunctional organocatalysts as they gave the products in very good diastereoselectivity and high enantioselectivity. In particular, the C6' sulfonamides catalyzed the reaction with the α,β-unsaturated α-amino acid derivatives to afford the products in a diastereomeric ratio as good as 93:7, with the major isomer being formed in an ee of up to 99%. The products of the organocatalytic sulfa-Michael addition to α,β-unsaturated α-amino acid derivatives were subsequently converted in high yields to enantiopure β-functionalized cysteines suitable for native chemical ligation.

  18. Extraordinary properties of functional integrals and groups of diffeomorphisms

    NASA Astrophysics Data System (ADS)

    Belokurov, V. V.; Shavgulidze, E. T.

    2017-03-01

    A review of the work of the authors is presented, in which corollaries of the quasi-invariance of functional integrals on the Wiener measure with respect to the action of a group of diffeomorphisms are studied, and the behavior of functional integrals with nonlinear nonlocal change of variables of integration is investigated as well. Using these substitutions, the functional integrals over discontinuous paths can be determined. The simplest models of the (Euclidean) quantum field theory are offered, in which the presence of hidden internal symmetries or the allowance for discontinuous paths in functional integrals leads to a number of paradoxical properties contradicting the conventional view.

  19. Nano- and Microgels Through Addition Reactions of Functional Oligomers and Polymers

    NASA Astrophysics Data System (ADS)

    Albrecht, Krystyna; Moeller, Martin; Groll, Juergen

    Nano- and Microgels are predominantly prepared using radical polymerization techniques. This chapter reviews alternative approaches to microgel preparation based on addition reactions of functional oligomers and polymers. This allows preparation of microgels under physiological conditions and in the presence of biologically active molecules without affecting their function. This method is therefore predominantly used to synthesize microgels for biomedical applications. Different crosslinking chemistries that have been used in this context are presented and discussed with regard to reaction conditions and stability of the reaction product. Microgels that have been prepared by these techniques are divided into two groups. Natural polymers used for the preparation of microgels are described first, followed by artificial prepolymers that are suitable for the preparation of microgels. The different preparation methods as well as the resulting microgels and their properties are presented and discussed.

  20. Additional duplicated Hox genes in the earthworm: Perionyx excavatus Hox genes consist of eleven paralog groups.

    PubMed

    Cho, Sung-Jin; Vallès, Yvonne; Kim, Kyong Min; Ji, Seong Chul; Han, Seock Jung; Park, Soon Cheol

    2012-02-10

    Annelida is a lophotrochozoan phylum whose members have a high degree of diversity in body plan morphology, reproductive strategies and ecological niches among others. Of the two traditional classes pertaining to the phylum Annelida (Polychaete and Clitellata), the structure and function of the Hox genes has not been clearly defined within the Oligochaeta class. Using a PCR-based survey, we were able to identify five new Hox genes from the earthworm Perionyx excavatus: a Hox3 gene (Pex-Hox3b), two Dfd genes (Pex-Lox6 and Pex-Lox18), and two posterior genes (Pex-post1 and -post2a). Our result suggests that the eleven earthworm Hox genes contain at least four paralog groups (PG) that have duplicated. We found the clitellates-diagnostic signature residues and annelid signature motif. Also, we show by semi-quantitative RT-PCR that duplicated Hox gene orthologs are differentially expressed in six different anterior-posterior body regions. These results provide essential data for comparative evolution of the Hox cluster within the Annelida.

  1. A group additivity algorithm for polychlorinated dibenzofurans derived from selected DFT analyses.

    PubMed

    Thompson, Dennis; Ewan, Bruce C R

    2007-06-14

    The difficulty in measuring the heats of combustion of polychlorinated dibenzofurans (PCDFs) has resulted in a shortage of data on their heats of formation, required for the purpose of developing an understanding of the role of thermodynamics and kinetics in their production via industrial processes. B3LYP density functional theory calculations have been carried out on a number of PCDFs using 6-31G(d) and 6-311+G(3df,p) basis sets to estimate their heats of formation based on the known experimental values for dibenzofuran, benzene and chlorobenzene. By examining the interactions among chlorine substituents, it is shown that energy contributions arising from successive chlorination can be interpreted in a predictable way, based on a small number of key energy parameters associated with ring position and chlorine atom repulsions. These parameters have been presented as the basis for a simplified prediction algorithm, which can be used to reproduce the predicted DFT heat of formation to within a few kJ/mol, avoiding the need to carry out extensive DFT calculations on the possible 135 isomers of the dibenzofuran group.

  2. Solving renormalization group equations with the Lambert W function

    NASA Astrophysics Data System (ADS)

    Sonoda, H.

    2013-04-01

    It has been known for some time that 2-loop renormalization group equations of a dimensionless parameter can be solved in a closed form in terms of the Lambert W function. We apply the method to a generic theory with a Gaussian fixed point to construct renormalization group invariant physical parameters such as a coupling constant and a physical squared mass. As a further application, we speculate a possible exact effective potential for the O(N) linear sigma model in four dimensions.

  3. Species, functional groups, and thresholds in ecological resilience

    USGS Publications Warehouse

    Sundstrom, Shana M.; Allen, Craig R.; Barichievy, Chris

    2012-01-01

    The cross-scale resilience model states that ecological resilience is generated in part from the distribution of functions within and across scales in a system. Resilience is a measure of a system's ability to remain organized around a particular set of mutually reinforcing processes and structures, known as a regime. We define scale as the geographic extent over which a process operates and the frequency with which a process occurs. Species can be categorized into functional groups that are a link between ecosystem processes and structures and ecological resilience. We applied the cross-scale resilience model to avian species in a grassland ecosystem. A species’ morphology is shaped in part by its interaction with ecological structure and pattern, so animal body mass reflects the spatial and temporal distribution of resources. We used the log-transformed rank-ordered body masses of breeding birds associated with grasslands to identify aggregations and discontinuities in the distribution of those body masses. We assessed cross-scale resilience on the basis of 3 metrics: overall number of functional groups, number of functional groups within an aggregation, and the redundancy of functional groups across aggregations. We assessed how the loss of threatened species would affect cross-scale resilience by removing threatened species from the data set and recalculating values of the 3 metrics. We also determined whether more function was retained than expected after the loss of threatened species by comparing observed loss with simulated random loss in a Monte Carlo process. The observed distribution of function compared with the random simulated loss of function indicated that more functionality in the observed data set was retained than expected. On the basis of our results, we believe an ecosystem with a full complement of species can sustain considerable species losses without affecting the distribution of functions within and across aggregations, although

  4. Psychosocial functioning of two groups of morbidly obese patients.

    PubMed

    Rosen, L W; Aniskiewicz, A S

    1983-01-01

    Fourteen morbidly obese women who were candidates for intestinal bypass surgery were compared in terms of psychosocial functioning and dietary behavior to 14 morbidly obese women who elected not to undergo the bypass procedure. Each patient underwent a psychiatric evaluation which included a developmental and dietary history, a mental status exam, and the administration of the MMPI. Diagnoses were based on the DSM-III multi-axial system. There was no difference between the bypass group and the non-bypass group on the Axis I diagnoses, however the bypass group did have a significantly higher frequency of Axis II diagnoses. The bypass group demonstrated significantly higher levels of psychosocial stressors (Axis IV) and lower levels of adaptive functioning (Axis V) when compared to the non-bypass group. The bypass patients also had a significantly higher frequency of past suicide attempts. On the MMPI, the bypass group had significantly higher elevations on scales 2 (depression), 4 (psychopathic deviate), 6 (paranoia), and 0 (social introversion). There were no significant differences between the groups in terms of dietary history and behavior, except that significantly fewer bypass patients could place a numerical estimate on their daily energy intake. These results were discussed in terms of their implications for the assessment and treatment of morbidly obese patients.

  5. Interactive effects between N addition and disturbance on boreal forest ecosystem structure and function

    NASA Astrophysics Data System (ADS)

    Nordin, Annika; Strengbom, Joachim; From, Fredrik

    2014-05-01

    In management of boreal forests, nitrogen (N) enrichment from atmospheric deposition or from forest fertilization can appear in combination with land-use related disturbances, i.e. tree harvesting by clear-felling. Long-term interactive effects between N enrichment and disturbance on boreal forest ecosystem structure and function are, however, poorly known. We investigated effects of N enrichment by forest fertilization done > 25 years ago on forest understory species composition in old-growth (undisturbed) forests, and in forests clear-felled 10 years ago (disturbed). In clear-felled forests we also investigated effects of the previous N addition on growth of tree saplings. The results show that the N enrichment effect on the understory species composition was strongly dependent on the disturbance caused by clear-felling. In undisturbed forests, there were small or no effects on understory species composition from N addition. In contrast, effects were large in forests first exposed to N addition and subsequently disturbed by clear-felling. Effects of N addition differed among functional groups of plants. Abundance of graminoids increased (+232%) and abundance of dwarf shrubs decreased (-44%) following disturbance in N fertilized forests. For vascular plants, the two perturbations had contrasting effects on α-(within forests) and β-diversity (among forests): in disturbed forests, N addition reduced, or had no effect on α-diversity, while β-diversity increased. For bryophytes, negative effects of disturbance on α-diversity were smaller in N fertilized forests than in forests not fertilized, while neither N addition nor disturbance had any effects on β-diversity. Moreover, sapling growth in forests clear-felled 10 years ago was significantly higher in previously N fertilized forests than in forests not fertilized. Our study show that effects of N addition on plant communities may appear small, short-lived, or even absent until exposed to a disturbance. This

  6. Victimization in the Peer Group and Children's Academic Functioning

    ERIC Educational Resources Information Center

    Schwartz, David; Gorman, Andrea Hopmeyer; Nakamoto, Jonathan; Toblin, Robin L.

    2005-01-01

    This short-term longitudinal investigation focused on associations between victimization in the peer group and academic functioning over a 1-year period. The authors used a multi-informant approach to assess peer victimization, symptoms of depression, and academic outcomes for 199 elementary school children (average age of 9.0 years; 105 boys, 94…

  7. Functional grouping in residential homes for people with intellectual disabilities.

    PubMed

    Mansell, Jim; Beadle-Brown, Julie; Macdonald, Susan; Ashman, Bev

    2003-01-01

    The effects of functional grouping of people with intellectual disabilities on care practices in small residential homes in the community were investigated. A group comparison and a matched-pairs comparison were carried out in settings where less than or more than 75% residents were non-verbal, non-ambulant, had severe challenging behaviour, severe social impairment or were verbal and ambulant. Further analysis, focused on those with challenging behaviour was carried out using ordinal regression. In the group-comparison study, no significant differences were found for three of the five groups. Residents who were non-ambulant were rated as receiving care with less interpersonal warmth in grouped settings; residents with severe challenging behaviour were rated as receiving less good care practices in four respects (interpersonal warmth, assistance from staff, level of speech and staff teamwork) in grouped settings. The matched-pairs comparison found significant differences only for people with challenging behaviour, where grouped settings achieved less good results in terms of interpersonal warmth and staff teamwork. Higher adaptive behaviour and mixed settings were predictive of better care practices on 13 of 14 items of the Active Support Measure (ASM), with some setting variables also predictive for some items. Care practices only appear to vary for people with challenging behaviour, where grouped settings appear to offer less good results in some respects.

  8. Linking functional group richness and ecosystem functions of dung beetles: an experimental quantification.

    PubMed

    Milotić, Tanja; Quidé, Stijn; Van Loo, Thomas; Hoffmann, Maurice

    2017-01-01

    Dung beetles form an insect group that fulfils important functions in terrestrial ecosystems throughout the world. These include nutrient cycling through dung removal, soil bioturbation, plant growth, secondary seed dispersal and parasite control. We conducted field experiments at two sites in the northern hemisphere temperate region in which dung removal and secondary seed dispersal were assessed. Dung beetles were classified in three functional groups, depending on their size and dung manipulation method: dwellers, large and small tunnelers. Other soil inhabiting fauna were included as a fourth functional group. Dung removal and seed dispersal by each individual functional group and combinations thereof were estimated in exclusion experiments using different dung types. Dwellers were the most diverse and abundant group, but tunnelers were dominant in terms of biomass. All dung beetle functional groups had a clear preference for fresh dung. The ecosystem services in dung removal and secondary seed dispersal provided by dung beetles were significant and differed between functional groups. Although in absolute numbers more dwellers were found, large tunnelers were disproportionally important for dung burial and seed removal. In the absence of dung beetles, other soil inhabiting fauna, such as earthworms, partly took over the dung decomposing role of dung beetles while most dung was processed when all native functional groups were present. Our results, therefore, emphasize the need to conserve functionally complete dung ecosystems to maintain full ecosystem functioning.

  9. Hydrolysis of organonitrate functional groups in aerosol particles

    SciTech Connect

    Liu, Shang; Shilling, John E.; Song, Chen; Hiranuma, Naruki; Zaveri, Rahul A.; Russell, Lynn M.

    2012-10-19

    Organonitrate (ON) groups are important substituents in secondary organic aerosols. Model simulations and laboratory studies indicate a large fraction of ON groups in aerosol particles, but much lower quantities are observed in the atmosphere. Hydrolysis of ON groups in aerosol particles has been proposed recently. To test this hypothesis, we simulated formation of ON molecules in a reaction chamber under a wide range of relative humidity (0% to 90%). The mass fraction of ON groups (5% to 20% for high-NOx experiments) consistently decreased with increasing relative humidity, which was best explained by hydrolysis of ON groups at a rate of 4 day-1 (lifetime of 6 hours) for reactions under relative humidity greater than 20%. In addition, we found that secondary nitrogen-containing molecules absorb light, with greater absorption under dry and high-NOx conditions. This work provides the first evidence for particle-phase hydrolysis of ON groups, a process that could substantially reduce ON group concentration in the atmosphere.

  10. Preparation and Characterization of Nanocomposite Polymer Membranes Containing Functionalized SnO2 Additives

    PubMed Central

    Scipioni, Roberto; Gazzoli, Delia; Teocoli, Francesca; Palumbo, Oriele; Paolone, Annalisa; Ibris, Neluta; Brutti, Sergio; Navarra, Maria Assunta

    2014-01-01

    In the research of new nanocomposite proton-conducting membranes, SnO2 ceramic powders with surface functionalization have been synthesized and adopted as additives in Nafion-based polymer systems. Different synthetic routes have been explored to obtain suitable, nanometer-sized sulphated tin oxide particles. Structural and morphological characteristics, as well as surface and bulk properties of the obtained oxide powders, have been determined by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier Transform Infrared (FTIR) and Raman spectroscopies, N2 adsorption, and thermal gravimetric analysis (TGA). In addition, dynamic mechanical analysis (DMA), atomic force microscopy (AFM), thermal investigations, water uptake (WU) measurements, and ionic exchange capacity (IEC) tests have been used as characterization tools for the nanocomposite membranes. The nature of the tin oxide precursor, as well as the synthesis procedure, were found to play an important role in determining the morphology and the particle size distribution of the ceramic powder, this affecting the effective functionalization of the oxides. The incorporation of such particles, having sulphate groups on their surface, altered some peculiar properties of the resulting composite membrane, such as water content, thermo-mechanical, and morphological characteristics. PMID:24957125

  11. 40 CFR 79.56 - Fuel and fuel additive grouping system.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ...-sponsored testing and analysis conducted on a product which is representative of all products in that group... nitroso-compounds; mixed nitro-compounds; mixed alkyl nitrates; mixed alkyl nitrites; peroxides;...

  12. 40 CFR 79.56 - Fuel and fuel additive grouping system.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-sponsored testing and analysis conducted on a product which is representative of all products in that group... nitroso-compounds; mixed nitro-compounds; mixed alkyl nitrates; mixed alkyl nitrites; peroxides;...

  13. 40 CFR 79.56 - Fuel and fuel additive grouping system.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ...-sponsored testing and analysis conducted on a product which is representative of all products in that group... nitroso-compounds; mixed nitro-compounds; mixed alkyl nitrates; mixed alkyl nitrites; peroxides;...

  14. 40 CFR 79.56 - Fuel and fuel additive grouping system.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-sponsored testing and analysis conducted on a product which is representative of all products in that group... nitroso-compounds; mixed nitro-compounds; mixed alkyl nitrates; mixed alkyl nitrites; peroxides;...

  15. 40 CFR 79.56 - Fuel and fuel additive grouping system.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-sponsored testing and analysis conducted on a product which is representative of all products in that group... nitroso-compounds; mixed nitro-compounds; mixed alkyl nitrates; mixed alkyl nitrites; peroxides;...

  16. [Identification of the functional groups of yeast thiamine pyrophosphokinase].

    PubMed

    Voskoboev, A I; Grinevich, V P

    1978-10-01

    The content of free sulfhydril groups in yeast thiamine pyrophosphokinase (EC 2.7.6.2) was studied. Their blocking was found not to affect considerably the enzyme activity. N-bromsuccinimide developes the inhibitory effect only if taken in excessive concentrations, which indicates that tryptophane has no key position for the enzyme-substrate complex formation. On account of high speed of photoinactivation with Rose bengale and methilene blue, sigmoid dependence of activity loss on pH under irradiation, characteristic narrowing of the modified enzyme absorption spectrum, it is suggested that imidazole residue of the histidine is one of the functional groups of thiamine pyrophosphokinase.

  17. Oxygen functional groups in graphitic carbon nitride for enhanced photocatalysis.

    PubMed

    Liu, Shizhen; Li, Degang; Sun, Hongqi; Ang, Ha Ming; Tadé, Moses O; Wang, Shaobin

    2016-04-15

    Metal-free semiconductors offer a new opportunity for environmental photocatalysis toward a potential breakthrough in high photo efficiency with complete prevention of metal leaching. In this study, graphitic carbon nitride (GCN) modified by oxygen functional groups was synthesized by a hydrothermal treatment of pristine GCN at different temperatures with H2O2. Insights into the emerging characteristics of the modified GCN in photocatalysis were obtained by determining the optical properties, band structure, electrochemical activity and pollutant degradation efficiency. It was found that the introduction of GCN with oxygen functional groups can enhance light absorption and accelerate electron transfer so as to improve the photocatalytic reaction efficiency. The photoinduced reactive radicals and the associated photodegradation were investigated by in situ electron paramagnetic resonance (EPR). The reactive radicals, O2(-) and OH, were responsible for organic degradation.

  18. Functional group dependent dissociative electron attachment to simple organic molecules

    NASA Astrophysics Data System (ADS)

    Prabhudesai, Vaibhav S.; Nandi, Dhananjay; Kelkar, Aditya H.; Krishnakumar, E.

    2008-04-01

    Dissociative electron attachment (DEA) cross sections for simple organic molecules, namely, acetic acid, propanoic acid, methanol, ethanol, and n-propyl amine are measured in a crossed beam experiment. We find that the H- ion formation is the dominant channel of DEA for these molecules and takes place at relatively higher energies (>4eV) through the core excited resonances. Comparison of the cross sections of the H- channel from these molecules with those from NH3, H2O, and CH4 shows the presence of functional group dependence in the DEA process. We analyze this new phenomenon in the context of the results reported on other organic molecules. This discovery of functional group dependence has important implications such as control in electron induced chemistry and understanding radiation induced damage in biological systems.

  19. A quantum chemical study of the mechanisms of olefin addition to group 9 transition metal dioxo compounds.

    PubMed

    Ahmed, Issahaku; Tia, Richard; Adei, Evans

    2016-01-01

    The mechanistic aspects of ethylene addition to MO2(CH2)(CH3) (M=Co, Rh, Ir) have been investigated with a Hartree-Fock/DFT hybrid functional at the MO6/LACVP* and B3LYP/LACVP* levels of theory to elucidate the reaction pathways on the singlet, doublet and triplet potential energy surfaces (PES). In the reaction of the IrO2CH2CH3 complex with ethylene, [3 + 2]C,O addition is the most plausible pathway on the singlet PES, the [3 + 2]O,O addition is the most favoured pathway on the doublet surface whiles the stepwise [1 + 1] addition involving the oxygen atom of the complex in the first step and the carbon atom of the complex in the second step is the most plausible pathway on the triplet PES. For the reaction of the RhO2(CH2)(CH3) complex, the [2 + 2]Rh,O addition pathway is the most favoured on the singlet surface, the [2 + 2]Rh,C is the most plausible pathway on the triplet PES and [3 + 2]C,O is the most plausible on the doublet surface. For the reactions of the CoO2(CH2)(CH3) complex, the [1 + 2]O addition is the most plausible on the singlet PES, [3 + 2]C=Co=O cycloaddition to form the five-membered intermediate is the most preferred pathway on the doublet PES, whiles on the triplet PES the preferred pathway is the [3 + 2] addition across the O=Co=O bond of the metal complex. The reactions of olefins with the Co dioxo complex have lower activation barriers for the preferred [3 + 2] and [2 + 2] addition pathways as well as fewer side reactions than those of the rhodium and iridium systems. This could imply that the cobalt dioxo complexes can efficiently and selectively catalyze specific reactions in oxidation of olefins than Rh and Ir oxo complexes will do and therefore Co oxo complexes may be better catalysts for specific oxidation reactions of olefins than Rh and Ir complexes are. The activation barriers for the formation of the four-or five-membered metallacycle intermediates through [2 + 2] or [3 + 2] cyclo-addition are lower on the

  20. Additional Validity Evidence and Across-Group Equivalency of the "HOPE Teacher Rating Scale"

    ERIC Educational Resources Information Center

    Peters, Scott J.; Gentry, Marcia

    2013-01-01

    The "HOPE Scale" was developed to identify academic and social components of giftedness and talent in elementary-aged students with particular attention to students from low-income and/or culturally diverse families. Based on previous findings, additional research was conducted on revisions made to the "HOPE Scale". Items were…

  1. Keldysh functional renormalization group for electronic properties of graphene

    NASA Astrophysics Data System (ADS)

    Fräßdorf, Christian; Mosig, Johannes E. M.

    2017-03-01

    We construct a nonperturbative nonequilibrium theory for graphene electrons interacting via the instantaneous Coulomb interaction by combining the functional renormalization group method with the nonequilibrium Keldysh formalism. The Coulomb interaction is partially bosonized in the forward scattering channel resulting in a coupled Fermi-Bose theory. Quantum kinetic equations for the Dirac fermions and the Hubbard-Stratonovich boson are derived in Keldysh basis, together with the exact flow equation for the effective action and the hierarchy of one-particle irreducible vertex functions, taking into account a possible nonzero expectation value of the bosonic field. Eventually, the system of equations is solved approximately under thermal equilibrium conditions at finite temperature, providing results for the renormalized Fermi velocity and the static dielectric function, which extends the zero-temperature results of Bauer et al., Phys. Rev. B 92, 121409 (2015), 10.1103/PhysRevB.92.121409.

  2. Functional renormalization group for the U (1 )-T56 tensorial group field theory with closure constraint

    NASA Astrophysics Data System (ADS)

    Lahoche, Vincent; Ousmane Samary, Dine

    2017-02-01

    This paper is focused on the functional renormalization group applied to the T56 tensor model on the Abelian group U (1 ) with closure constraint. For the first time, we derive the flow equations for the couplings and mass parameters in a suitable truncation around the marginal interactions with respect to the perturbative power counting. For the second time, we study the behavior around the Gaussian fixed point, and show that the theory is nonasymptotically free. Finally, we discuss the UV completion of the theory. We show the existence of several nontrivial fixed points, study the behavior of the renormalization group flow around them, and point out evidence in favor of an asymptotically safe theory.

  3. Characterization of Sea Lettuce Surface Functional Groups by Potentiometric Titrations

    NASA Astrophysics Data System (ADS)

    Ebling, A. M.; Schijf, J.

    2008-12-01

    In pursuit of our ultimate goal to better understand the prodigious capacity of the marine macroalga Ulva lactuca (sea lettuce) for adsorbing a broad range of dissolved trace metals from seawater, we performed an initial characterization of its surface functional groups. Specifically, the number of distinct functional groups as well as their individual bulk concentrations and acid dissociation constants (pKas) were determined by potentiometric titrations in NaCl solutions of various ionic strengths (I = 0.01-5.0 M), under inert nitrogen atmosphere at 25°C. Depending on the ionic strength, Ulva samples were manually titrated down to pH 2 or 3 with 1 N HCl and then up to pH 10 with 1 N NaOH in steps of 0.1-0.2 units, continuously monitoring pH with a glass combination electrode. Titrations of a dehydrated Ulva standard reference material (BCR-279) were compared with fresh Ulva tissue cultured in our laboratory. A titration in filtered natural seawater was also compared with one in an NaCl solution of equal ionic strength. Equilibrium constants for the ionization of water in NaCl solutions as a function of ionic strength were obtained from the literature. Fits to the titration data ([H]T vs. pH) were performed with the FITEQL4.0 computer code using non-electrostatic 3-, 4-, and 5-site models, either by fixing ionic strength at its experimental value or by allowing it to be extrapolated to zero, while considering all functional group pKas and bulk concentrations as adjustable parameters. Since pKas and bulk concentrations were found to be strongly correlated, the latter were also fixed in some cases to further constrain the pKas. Whereas these calculations are currently ongoing, preliminary results point to three, possibly four, functional groups with pKas of about 4.1, 6.3, and 9.5 at I = 0. Bulk concentrations of the three groups are very similar, about 5-6×10-4 mol/g based on dry weight, which suggests that all are homogeneously distributed over the surface and

  4. Catalytic Addition of Simple Alkenes to Carbonyl Compounds Using Group 10 Metals

    PubMed Central

    Schleicher, Kristin D.

    2011-01-01

    Recent advances using nickel complexes in the activation of unactivated monosubstituted olefins for catalytic intermolecular carbon–carbon bond-forming reactions with carbonyl compounds, such as simple aldehydes, isocyanates, and conjugated aldehydes and ketones, are discussed. In these reactions, the olefins function as vinyl- and allylmetal equivalents, providing a new strategy for organic synthesis. Current limitations and the outlook for this new strategy are also discussed. PMID:21904421

  5. Organized thiol functional groups in mesoporous core shell colloids

    SciTech Connect

    Marchena, Martin H.; Granada, Mara; Bordoni, Andrea V.; Joselevich, Maria; Troiani, Horacio; Williams, Federico J.; Wolosiuk, Alejandro

    2012-03-15

    The co-condensation in situ of tetraethoxysilane (TEOS) and mercaptopropyltrimethoxysilane (MPTMS) using cetyltrimethylammonium bromide (CTAB) as a template results in the synthesis of multilayered mesoporous structured SiO{sub 2} colloids with 'onion-like' chemical environments. Thiol groups were anchored to an inner selected SiO{sub 2} porous layer in a bilayered core shell particle producing different chemical regions inside the colloidal layered structure. X-Ray Photoelectron Spectroscopy (XPS) shows a preferential anchoring of the -SH groups in the double layer shell system, while porosimetry and simple chemical modifications confirm that pores are accessible. We can envision the synthesis of interesting colloidal objects with defined chemical environments with highly controlled properties. - Graphical abstract: Mesoporous core shell SiO{sub 2} colloids with organized thiol groups. Highlights: Black-Right-Pointing-Pointer Double shell mesoporous silica colloids templated with CTAB. Black-Right-Pointing-Pointer Sequential deposition of mesoporous SiO{sub 2} layers with different chemistries. Black-Right-Pointing-Pointer XPS shows the selective functionalization of mesoporous layers with thiol groups.

  6. Finding sequence motifs in groups of functionally related proteins.

    PubMed

    Smith, H O; Annau, T M; Chandrasegaran, S

    1990-01-01

    We have developed a method for rapidly finding patterns of conserved amino acid residues (motifs) in groups of functionally related proteins. All 3-amino acid patterns in a group of proteins of the type aa1 d1 aa2 d2 aa3, where d1 and d2 are distances that can be varied in a range up to 24 residues, are accumulated into an array. Segments of the proteins containing those patterns that occur most frequently are aligned on each other by a scoring method that obtains an average relatedness value for all the amino acids in each column of the aligned sequence block based on the Dayhoff relatedness odds matrix. The automated method successfully finds and displays nearly all of the sequence motifs that have been previously reported to occur in 33 reverse transcriptases, 18 DNA integrases, and 30 DNA methyltransferases.

  7. Selective behavioral alterations on addition of a 4'-phenyl group to cocaine.

    PubMed

    Seale, T W; Niekrasz, I; Chang, F; Singh, S; Basmadjian, G P

    1996-01-31

    We synthesized a cocaine analog in which a phenyl group was added at the para-position of the benzene ring of cocaine. This substitution caused a modest reduction (four-fold compared with cocaine) in binding potency for the primate (Papio) dopamine transporter as judged by displacement of [3H]WIN 35,428 binding from caudate/putamen membranes. Behavioral effects of this structural modification in the mouse were complex and selective, comprising absence of stimulation of locomotor activity, enhanced inhibition of locomotion and reduced lethal potency. Convulsant potency was unaltered. Substituents at the 4'-position of cocaine are important in its actions. Simple changes in the chemical structure of this drug may produce complex and selective changes in its neurochemical and behavioral actions.

  8. Functional renormalization group study of nuclear and neutron matter

    SciTech Connect

    Drews, Matthias; Weise, Wolfram

    2016-01-22

    A chiral model based on nucleons interacting via boson exchange is investigated. Fluctuation effects are included consistently beyond the mean-field approximation in the framework of the functional renormalization group. The liquid-gas phase transition of symmetric nuclear matter is studied in detail. No sign of a chiral restoration transition is found up to temperatures of about 100 MeV and densities of at least three times the density of normal nuclear matter. Moreover, the model is extended to asymmetric nuclear matter and the constraints from neutron star observations are discussed.

  9. Activity related to the carcinogenicity of plastic additives in the benzophenone group.

    PubMed

    Nakajima, Daisuke; Asada, Shin; Kageyama, Shiho; Yamamoto, Takashi; Kuramochi, Hidetoshi; Tanaka, Noriho; Takeda, Ken; Goto, Sumio

    2006-06-01

    This study examines the activities relating to the carcinogenicity of six types of benzophenone derivatives (benzophenone, 2-hydroxy-4-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and 2,2'-dihydroxy-4,4'-dimethoxybenzophenone) currently used in plastic products as additives to serve as ultraviolet absorbing agents. The evaluation of the initiation activity used a light absorption umu-test, a luminescent umu-test and the Ames test. The promotion activity was examined by a Bhas assay, a method that uses Bhas 42 cells for the formation of transformation foci. The luminescent umu-test indicated positive initiation activity of 2-hydroxy-4-methoxybenzophenone, and pseudo-positive activity of 2,4-dihydroxybenzophenone and 2,2'-dihydroxy-4-methoxybenzophenone. In the Ames test, 2-hydroxy-4-octyloxybenzophenone showed pseudo-positive initiation activity. Conversely, 2,4-dihydroxybenzophenone indicated weak promotion activity at 10 microg/ml concentration.

  10. ESG: extended similarity group method for automated protein function prediction

    PubMed Central

    Chitale, Meghana; Hawkins, Troy; Park, Changsoon; Kihara, Daisuke

    2009-01-01

    Motivation: Importance of accurate automatic protein function prediction is ever increasing in the face of a large number of newly sequenced genomes and proteomics data that are awaiting biological interpretation. Conventional methods have focused on high sequence similarity-based annotation transfer which relies on the concept of homology. However, many cases have been reported that simple transfer of function from top hits of a homology search causes erroneous annotation. New methods are required to handle the sequence similarity in a more robust way to combine together signals from strongly and weakly similar proteins for effectively predicting function for unknown proteins with high reliability. Results: We present the extended similarity group (ESG) method, which performs iterative sequence database searches and annotates a query sequence with Gene Ontology terms. Each annotation is assigned with probability based on its relative similarity score with the multiple-level neighbors in the protein similarity graph. We will depict how the statistical framework of ESG improves the prediction accuracy by iteratively taking into account the neighborhood of query protein in the sequence similarity space. ESG outperforms conventional PSI-BLAST and the protein function prediction (PFP) algorithm. It is found that the iterative search is effective in capturing multiple-domains in a query protein, enabling accurately predicting several functions which originate from different domains. Availability: ESG web server is available for automated protein function prediction at http://dragon.bio.purdue.edu/ESG/ Contact: cspark@cau.ac.kr; dkihara@purdue.edu Supplementary information: Supplementary data are available at Bioinformatics online. PMID:19435743

  11. Additive opportunistic capture explains group hunting benefits in African wild dogs.

    PubMed

    Hubel, Tatjana Y; Myatt, Julia P; Jordan, Neil R; Dewhirst, Oliver P; McNutt, J Weldon; Wilson, Alan M

    2016-03-29

    African wild dogs (Lycaon pictus) are described as highly collaborative endurance pursuit hunters based on observations derived primarily from the grass plains of East Africa. However, the remaining population of this endangered species mainly occupies mixed woodland savannah where hunting strategies appear to differ from those previously described. We used high-resolution GPS and inertial technology to record fine-scale movement of all members of a single pack of six adult African wild dogs in northern Botswana. The dogs used multiple short-distance hunting attempts with a low individual kill rate (15.5%), but high group feeding rate due to the sharing of prey. Use of high-level cooperative chase strategies (coordination and collaboration) was not recorded. In the mixed woodland habitats typical of their current range, simultaneous, opportunistic, short-distance chasing by dogs pursuing multiple prey (rather than long collaborative pursuits of single prey by multiple individuals) could be the key to their relative success in these habitats.

  12. Additive opportunistic capture explains group hunting benefits in African wild dogs

    PubMed Central

    Hubel, Tatjana Y.; Myatt, Julia P.; Jordan, Neil R.; Dewhirst, Oliver P.; McNutt, J. Weldon; Wilson, Alan M.

    2016-01-01

    African wild dogs (Lycaon pictus) are described as highly collaborative endurance pursuit hunters based on observations derived primarily from the grass plains of East Africa. However, the remaining population of this endangered species mainly occupies mixed woodland savannah where hunting strategies appear to differ from those previously described. We used high-resolution GPS and inertial technology to record fine-scale movement of all members of a single pack of six adult African wild dogs in northern Botswana. The dogs used multiple short-distance hunting attempts with a low individual kill rate (15.5%), but high group feeding rate due to the sharing of prey. Use of high-level cooperative chase strategies (coordination and collaboration) was not recorded. In the mixed woodland habitats typical of their current range, simultaneous, opportunistic, short-distance chasing by dogs pursuing multiple prey (rather than long collaborative pursuits of single prey by multiple individuals) could be the key to their relative success in these habitats. PMID:27023355

  13. FTIR Analysis of Functional Groups in Aerosol Particles

    NASA Astrophysics Data System (ADS)

    Shokri, S. M.; McKenzie, G.; Dransfield, T. J.

    2012-12-01

    Secondary organic aerosols (SOA) are suspensions of particulate matter composed of compounds formed from chemical reactions of organic species in the atmosphere. Atmospheric particulate matter can have impacts on climate, the environment and human health. Standardized techniques to analyze the characteristics and composition of complex secondary organic aerosols are necessary to further investigate the formation of SOA and provide a better understanding of the reaction pathways of organic species in the atmosphere. While Aerosol Mass Spectrometry (AMS) can provide detailed information about the elemental composition of a sample, it reveals little about the chemical moieties which make up the particles. This work probes aerosol particles deposited on Teflon filters using FTIR, based on the protocols of Russell, et al. (Journal of Geophysical Research - Atmospheres, 114, 2009) and the spectral fitting algorithm of Takahama, et al (submitted, 2012). To validate the necessary calibration curves for the analysis of complex samples, primary aerosols of key compounds (e.g., citric acid, ammonium sulfate, sodium benzoate) were generated, and the accumulated masses of the aerosol samples were related to their IR absorption intensity. These validated calibration curves were then used to classify and quantify functional groups in SOA samples generated in chamber studies by MIT's Kroll group. The fitting algorithm currently quantifies the following functionalities: alcohols, alkanes, alkenes, amines, aromatics, carbonyls and carboxylic acids.

  14. Anaerobic Activation of p-Cymene in Denitrifying Betaproteobacteria: Methyl Group Hydroxylation versus Addition to Fumarate

    PubMed Central

    Strijkstra, Annemieke; Trautwein, Kathleen; Jarling, René; Wöhlbrand, Lars; Dörries, Marvin; Reinhardt, Richard; Drozdowska, Marta; Golding, Bernard T.; Wilkes, Heinz

    2014-01-01

    The betaproteobacteria “Aromatoleum aromaticum” pCyN1 and “Thauera” sp. strain pCyN2 anaerobically degrade the plant-derived aromatic hydrocarbon p-cymene (4-isopropyltoluene) under nitrate-reducing conditions. Metabolite analysis of p-cymene-adapted “A. aromaticum” pCyN1 cells demonstrated the specific formation of 4-isopropylbenzyl alcohol and 4-isopropylbenzaldehyde, whereas with “Thauera” sp. pCyN2, exclusively 4-isopropylbenzylsuccinate and tentatively identified (4-isopropylphenyl)itaconate were observed. 4-Isopropylbenzoate in contrast was detected with both strains. Proteogenomic investigation of p-cymene- versus succinate-adapted cells of the two strains revealed distinct protein profiles agreeing with the different metabolites formed from p-cymene. “A. aromaticum” pCyN1 specifically produced (i) a putative p-cymene dehydrogenase (CmdABC) expected to hydroxylate the benzylic methyl group of p-cymene, (ii) two dehydrogenases putatively oxidizing 4-isopropylbenzyl alcohol (Iod) and 4-isopropylbenzaldehyde (Iad), and (iii) the putative 4-isopropylbenzoate-coenzyme A (CoA) ligase (Ibl). The p-cymene-specific protein profile of “Thauera” sp. pCyN2, on the other hand, encompassed proteins homologous to subunits of toluene-activating benzylsuccinate synthase (termed [4-isopropylbenzyl]succinate synthase IbsABCDEF; identified subunits, IbsAE) and protein homologs of the benzylsuccinate β-oxidation (Bbs) pathway (termed BisABCDEFGH; all identified except for BisEF). This study reveals that two related denitrifying bacteria employ fundamentally different peripheral degradation routes for one and the same substrate, p-cymene, with the two pathways apparently converging at the level of 4-isopropylbenzoyl-CoA. PMID:25261521

  15. Polyethylene glycol addition does not improve exogenous surfactant function in an experimental model of meconium aspiration syndrome.

    PubMed

    Lyra, Joao Cesar; Mascaretti, Renata Suman; Precioso, Alexander Roberto; Haddad, Luciana Branco; Mauad, Thais; Vaz, Flavio A Costa; Rebello, Celso Moura

    2009-02-01

    Meconium (MEC) is a potent inactivator of pulmonary surfactant. The authors studied the effects of polyethylene glycol addition to the exogenous surfactant over the lung mechanics and volumes. Human meconium was administrated to newborn rabbits. Animals were ventilated for 20 minutes and dynamic compliance, ventilatory pressure, and tidal volume were recorded. Animals were randomized into 3 study groups: MEC group (without surfactant therapy); S100 group (100 mg/kg surfactant); and PEG group (100 mg/kg porcine surfactant plus 5% PEG). After ventilation, a pulmonary pressure-volume curve was built. Histological analysis was carried out to calculate the mean alveolar size (Lm) and the distortion index (DI). Both groups treated with surfactant showed higher values of dynamic pulmonary compliance and lower ventilatory pressure, compared with the MEC group (P < .05). S100 group had a larger maximum lung volume, V(30), compared with the MEC group (P < .05). Lm and DI values were smaller in the groups treated with surfactant than in the MEC group (P < .05). No differences were observed between the S100 and PEG groups. Animals treated with surfactant showed significant improvement in pulmonary function as compared to nontreated animals. PEG added to exogenous surfactant did not improve lung mechanics or volumes.

  16. Slow-binding inhibitors of prolyl oligopeptidase with different functional groups at the P1 site.

    PubMed

    Venäläinen, Jarkko I; Juvonen, Risto O; Garcia-Horsman, J Arturo; Wallén, Erik A A; Christiaans, Johannes A M; Jarho, Elina M; Gynther, Jukka; Männistö, Pekka T

    2004-09-15

    POP (prolyl oligopeptidase) specifically hydrolyses a number of small proline-containing peptides at the carboxy end of the proline residue and POP inhibitors have been shown to have cognition-enhancing properties. It has been noted that certain functional groups at the P1 site of the inhibitor, which correspond to the substrate residue on the N-terminal side of the bond to be cleaved, increase the inhibitory potency. However, detailed mechanistic and kinetic analysis of the inhibition has not been studied. In the present study, we examined the effect of different functional groups at the P1 site of the parent inhibitor isophthalic acid bis-(L-prolylpyrrolidine) amide on the binding kinetics to POP. Addition of CHO, CN or COCH(2)OH groups to the P1 site increased the inhibitory potency by two orders of magnitude (K(i)=11.8-0.1 nM) and caused a clear slow-binding inhibition. The inhibitor containing a CHO group had the lowest association rate constant, k(on)=(2.43+/-0.12) x 10(5) M(-1) x s(-1), whereas the inhibitor with a CN group exhibited the fastest binding, k(on)=(12.0+/-0.08)x10(5) M(-1) x s(-1). In addition, the dissociation rate was found to be crucially dependent on the type of the functional group. Compounds with COCH(2)OH and CHO groups had much longer half-lives of dissociation (over 5 h) compared with the compound with the CN group (25 min), although the K(i) values of the compounds were relatively similar. A possibility to optimize the duration of inhibition by changing the functional group at the P1 site is important when planning therapeutically useful POP inhibitors.

  17. Bicyclo[3.2.1]octane synthons from cyclopropenes: functionalization of cycloadducts by nucleophilic additions.

    PubMed

    Orugunty, Ravi S; Wright, Dennis L; Battiste, Merle A; Helmich, Richard J; Abboud, Khalil

    2004-01-23

    It has been known for several decades that a highly functionalized family of tetrahalobicyclo[3.2.1]octadienes are readily available through the cycloaddition of furan or cyclopentadiene with either tetrachloro- or tetrabromocyclopropene. However, the application of these highly functionalized building blocks in synthesis has remained relatively unexplored in relation to their better-known counterparts derived through oxyallyl cation additions. As a first step toward utilizing these highly versatile intermediates in synthesis, a study of the addition of various nucleophiles to the halogenated nucleus has been conducted. It has been found that these halogenated systems are amenable to a wide range of functionalizations in high yields and with good selectivities.

  18. Exopolysaccharide from Lactobacillus fermentum Lf2 and its functional characterization as a yogurt additive.

    PubMed

    Ale, Elisa C; Perezlindo, Marcos J; Burns, Patricia; Tabacman, Eduardo; Reinheimer, Jorge A; Binetti, Ana G

    2016-11-01

    Lactobacillus fermentum Lf2 is a strain which is able to produce high levels (approximately 1 g/l) of crude exopolysaccharide (EPS) when it is grown in optimised conditions. The aim of this work was to characterize the functional aspects of this EPS extract, focusing on its application as a dairy food additive. Our findings are consistent with an EPS extract that acts as moderate immunomodulator, modifying s-IgA and IL-6 levels in the small intestine when added to yogurt and milk, respectively. Furthermore, this EPS extract, in a dose feasible to use as a food additive, provides protection against Salmonella infection in a murine model, thus representing a mode of action to elicit positive health benefits. Besides, it contributes to the rheological characteristics of yogurt, and could function as a food additive with both technological and functional roles, making possible the production of a new functional yogurt with improved texture.

  19. In-medium spectral functions of vector- and axial-vector mesons from the functional renormalization group

    NASA Astrophysics Data System (ADS)

    Jung, Christopher; Rennecke, Fabian; Tripolt, Ralf-Arno; von Smekal, Lorenz; Wambach, Jochen

    2017-02-01

    In this work, we present the first results on vector- and axial-vector meson spectral functions as obtained by applying the nonperturbative functional renormalization group approach to an effective low-energy theory motivated by the gauged linear sigma model. By using a recently proposed analytic continuation method, we study the in-medium behavior of the spectral functions of the ρ and a1 mesons in different regimes of the phase diagram. In particular, we demonstrate explicitly how these spectral functions degenerate at high temperatures as well as at large chemical potentials, as a consequence of the restoration of chiral symmetry. In addition, we also compute the momentum dependence of the ρ and a1 spectral functions and discuss the various timelike and spacelike processes that can occur.

  20. Nutrient resorption patterns of plant functional groups in a tropical savanna: variation and functional significance.

    PubMed

    Ratnam, Jayashree; Sankaran, Mahesh; Hanan, Niall P; Grant, Rina C; Zambatis, Nick

    2008-08-01

    Green and senesced leaf nitrogen (N) and phosphorus (P) concentrations of different plant functional groups in savanna communities of Kruger National Park, South Africa were analyzed to determine if nutrient resorption was regulated by plant nutritional status and foliar N:P ratios. The N and P concentrations in green leaves and the N concentrations in senesced leaves differed significantly between the dominant plant functional groups in these savannas: fine-leaved trees, broad-leaved trees and grasses. However, all three functional groups reduced P to comparable and very low levels in senesced leaves, suggesting that P was tightly conserved in this tropical semi-arid savanna ecosystem. Across all functional groups, there was evidence for nutritional control of resorption in this system, with both N and P resorption efficiencies decreasing as green leaf nutrient concentrations increased. However, specific patterns of resorption and the functional relationships between nutrient concentrations in green and senesced leaves varied by nutrient and plant functional group. Functional relationships between N concentrations in green and senesced leaves were indistinguishable between the dominant groups, suggesting that variation in N resorption efficiency was largely the result of inter-life form differences in green leaf N concentrations. In contrast, observed differences in P resorption efficiencies between life forms appear to be the result of both differences in green leaf P concentrations as well as inherent differences between life forms in the fraction of green leaf P resorbed from senescing leaves. Our results indicate that foliar N:P ratios are poor predictors of resorption efficiency in this ecosystem, in contrast to N and P resorption proficiencies, which are more responsive to foliar N:P ratios.

  1. Correlation functions from a unified variational principle: Trial Lie groups

    SciTech Connect

    Balian, R.; Vénéroni, M.

    2015-11-15

    Time-dependent expectation values and correlation functions for many-body quantum systems are evaluated by means of a unified variational principle. It optimizes a generating functional depending on sources associated with the observables of interest. It is built by imposing through Lagrange multipliers constraints that account for the initial state (at equilibrium or off equilibrium) and for the backward Heisenberg evolution of the observables. The trial objects are respectively akin to a density operator and to an operator involving the observables of interest and the sources. We work out here the case where trial spaces constitute Lie groups. This choice reduces the original degrees of freedom to those of the underlying Lie algebra, consisting of simple observables; the resulting objects are labeled by the indices of a basis of this algebra. Explicit results are obtained by expanding in powers of the sources. Zeroth and first orders provide thermodynamic quantities and expectation values in the form of mean-field approximations, with dynamical equations having a classical Lie–Poisson structure. At second order, the variational expression for two-time correlation functions separates–as does its exact counterpart–the approximate dynamics of the observables from the approximate correlations in the initial state. Two building blocks are involved: (i) a commutation matrix which stems from the structure constants of the Lie algebra; and (ii) the second-derivative matrix of a free-energy function. The diagonalization of both matrices, required for practical calculations, is worked out, in a way analogous to the standard RPA. The ensuing structure of the variational formulae is the same as for a system of non-interacting bosons (or of harmonic oscillators) plus, at non-zero temperature, classical Gaussian variables. This property is explained by mapping the original Lie algebra onto a simpler Lie algebra. The results, valid for any trial Lie group, fulfill

  2. Glucose dehydrogenase polymorphism among ethnic groups of Singapore--with report of two additional alleles (GDH4 and GDH5).

    PubMed

    Saha, N; Bhattacharyya, S P; Yeoh, S C; Chua, S P; Ratnam, S S

    1987-02-01

    Placental glucose dehydrogenase (GDH; E.C.1.1.1.47) polymorphism was studied in 254 Chinese, 104 Malays, and 47 Indians from Singapore using isoelectric focusing. There is suggestive evidence of two additional anodal alleles (GDH4 and GDH5) in addition to the three alleles described in earlier studies. Altogether, 14 phenotypes have been observed in the present investigation, compared with six phenotypes described in earlier studies. It appears that placental GDH is controlled by five codominant autosomal alleles producing 15 possible phenotypes. The gene frequencies of GDH1, GDH2, and GDH3 in these ethnic groups are significantly different from those reported in Caucasians. There were slight differences in the gene frequencies between the three ethnic groups, with those of Indians being nearer to the frequency in Caucasians. In general, the distribution of GDH phenotypes was at Hardy-Weinberg equilibrium in all three ethnic groups studied.

  3. Functional renormalization group studies of nuclear and neutron matter

    NASA Astrophysics Data System (ADS)

    Drews, Matthias; Weise, Wolfram

    2017-03-01

    Functional renormalization group (FRG) methods applied to calculations of isospin-symmetric and asymmetric nuclear matter as well as neutron matter are reviewed. The approach is based on a chiral Lagrangian expressed in terms of nucleon and meson degrees of freedom as appropriate for the hadronic phase of QCD with spontaneously broken chiral symmetry. Fluctuations beyond mean-field approximation are treated solving Wetterich's FRG flow equations. Nuclear thermodynamics and the nuclear liquid-gas phase transition are investigated in detail, both in symmetric matter and as a function of the proton fraction in asymmetric matter. The equations of state at zero temperature of symmetric nuclear matter and pure neutron matter are found to be in good agreement with advanced ab-initio many-body computations. Contacts with perturbative many-body approaches (in-medium chiral perturbation theory) are discussed. As an interesting test case, the density dependence of the pion mass in the medium is investigated. The question of chiral symmetry restoration in nuclear and neutron matter is addressed. A stabilization of the phase with spontaneously broken chiral symmetry is found to persist up to high baryon densities once fluctuations beyond mean-field are included. Neutron star matter including beta equilibrium is discussed under the aspect of the constraints imposed by the existence of two-solar-mass neutron stars.

  4. EFFECT OF FUNCTIONAL GROUP CONFORMATION ON THE INFRARED SPECTRA OF SOME GEM DIFUNCTIONAL PHENYLETHYLENE DERIVATIVES,

    DTIC Science & Technology

    each functional group . The two bands for similar functional groups have been ascribed to S-cis- and S-trans- conformations of the carbonyl groups with...Except for the benzalmalononitriles, two functional group stretching vibrations occur in the infrared (i.r.) spectra of the beta,beta-difunctional...styrenes with similar functional groups . For geometrically homogeneous compounds with dissimilar functional groups only one absorption band occurs for

  5. Observations of Adolescent Peer Group Interactions as a Function of Within- and Between-Group Centrality Status

    ERIC Educational Resources Information Center

    Ellis, Wendy E.; Dumas, Tara M.; Mahdy, Jasmine C.; Wolfe, David A.

    2012-01-01

    Observations of adolescent (n = 258; M age = 15.45) peer group triads (n = 86) were analyzed to identify conversation and interaction styles as a function of within-group and between-group centrality status. Group members' discussions about hypothetical dilemmas were coded for agreements, disagreements, commands, and opinions. Interactions during…

  6. Modification of Polymer Network Properties through the Addition of Functional Nanogel Particles

    NASA Astrophysics Data System (ADS)

    Liu, JianCheng

    Multifunctional acrylic and methacrylic monomers have been widely applied in many photopolymerization applications to produce crosslinked polymers with advantages such as rapid curing, broad choices of commercially available monomers and desirable physical and mechanical properties. However, there still remain critical challenges for these materials during polymerization including limited conversion and early onset of gelation as well as the generation of significant polymerization shrinkage and stress. This thesis explores the effects of network property modification through the addition of polymeric nanoparticles or nanogels. In order to understand the relationship between nanogel structure and composite material properties, nanogels with different architectures and functionalities were studied during polymerization in terms of kinetics, shrinkage and stress reduction, mechanical performance and reaction mechanisms. Nanogel composite formulations were evaluated to understand the interaction between nanogel structure with the resin matrix during polymerization through adjustment of nanogel branching densities and reactivity of polymer chain ends. It was found that both the chemical crosslinking from reactive chain ends and physical entanglements of high branching density nanogels with the resin matrix dramatically could improve final material mechanical strength. The reductions in overall volumetric shrinkage and shrinkage stress were found to follow at least proportional behavior with respect to nanogel loading concentration while maintaining similar final conversion and modulus results compared with the control resin. Nanogels containing unique functionalities were designed in order to modify reaction mechanism during secondary polymerization. A nanogel containing an integrated photoinitiator and active chain-end RAFT groups was able to initiate secondary polymerization from the nanogel phase so that localized polymerization was achieved from the beginning of

  7. Changes in bird functional diversity across multiple land uses: interpretations of functional redundancy depend on functional group identity.

    PubMed

    Luck, Gary W; Carter, Andrew; Smallbone, Lisa

    2013-01-01

    Examinations of the impact of land-use change on functional diversity link changes in ecological community structure driven by land modification with the consequences for ecosystem function. Yet, most studies have been small-scale, experimental analyses and primarily focussed on plants. There is a lack of research on fauna communities and at large-scales across multiple land uses. We assessed changes in the functional diversity of bird communities across 24 land uses aligned along an intensification gradient. We tested the hypothesis that functional diversity is higher in less intensively used landscapes, documented changes in diversity using four diversity metrics, and examined how functional diversity varied with species richness to identify levels of functional redundancy. Functional diversity, measured using a dendogram-based metric, increased from high to low intensity land uses, but observed values did not differ significantly from randomly-generated expected values. Values for functional evenness and functional divergence did not vary consistently with land-use intensification, although higher than expected values were mostly recorded in high intensity land uses. A total of 16 land uses had lower than expected values for functional dispersion and these were mostly low intensity native vegetation sites. Relations between functional diversity and bird species richness yielded strikingly different patterns for the entire bird community vs. particular functional groups. For all birds and insectivores, functional evenness, divergence and dispersion showed a linear decline with increasing species richness suggesting substantial functional redundancy across communities. However, for nectarivores, frugivores and carnivores, there was a significant hump-shaped or non-significant positive linear relationship between these functional measures and species richness indicating less redundancy. Hump-shaped relationships signify that the most functionally diverse

  8. Changes in Bird Functional Diversity across Multiple Land Uses: Interpretations of Functional Redundancy Depend on Functional Group Identity

    PubMed Central

    Luck, Gary W.; Carter, Andrew; Smallbone, Lisa

    2013-01-01

    Examinations of the impact of land-use change on functional diversity link changes in ecological community structure driven by land modification with the consequences for ecosystem function. Yet, most studies have been small-scale, experimental analyses and primarily focussed on plants. There is a lack of research on fauna communities and at large-scales across multiple land uses. We assessed changes in the functional diversity of bird communities across 24 land uses aligned along an intensification gradient. We tested the hypothesis that functional diversity is higher in less intensively used landscapes, documented changes in diversity using four diversity metrics, and examined how functional diversity varied with species richness to identify levels of functional redundancy. Functional diversity, measured using a dendogram-based metric, increased from high to low intensity land uses, but observed values did not differ significantly from randomly-generated expected values. Values for functional evenness and functional divergence did not vary consistently with land-use intensification, although higher than expected values were mostly recorded in high intensity land uses. A total of 16 land uses had lower than expected values for functional dispersion and these were mostly low intensity native vegetation sites. Relations between functional diversity and bird species richness yielded strikingly different patterns for the entire bird community vs. particular functional groups. For all birds and insectivores, functional evenness, divergence and dispersion showed a linear decline with increasing species richness suggesting substantial functional redundancy across communities. However, for nectarivores, frugivores and carnivores, there was a significant hump-shaped or non-significant positive linear relationship between these functional measures and species richness indicating less redundancy. Hump-shaped relationships signify that the most functionally diverse

  9. Highly adaptive tests for group differences in brain functional connectivity.

    PubMed

    Kim, Junghi; Pan, Wei

    2015-01-01

    Resting-state functional magnetic resonance imaging (rs-fMRI) and other technologies have been offering evidence and insights showing that altered brain functional networks are associated with neurological illnesses such as Alzheimer's disease. Exploring brain networks of clinical populations compared to those of controls would be a key inquiry to reveal underlying neurological processes related to such illnesses. For such a purpose, group-level inference is a necessary first step in order to establish whether there are any genuinely disrupted brain subnetworks. Such an analysis is also challenging due to the high dimensionality of the parameters in a network model and high noise levels in neuroimaging data. We are still in the early stage of method development as highlighted by Varoquaux and Craddock (2013) that "there is currently no unique solution, but a spectrum of related methods and analytical strategies" to learn and compare brain connectivity. In practice the important issue of how to choose several critical parameters in estimating a network, such as what association measure to use and what is the sparsity of the estimated network, has not been carefully addressed, largely because the answers are unknown yet. For example, even though the choice of tuning parameters in model estimation has been extensively discussed in the literature, as to be shown here, an optimal choice of a parameter for network estimation may not be optimal in the current context of hypothesis testing. Arbitrarily choosing or mis-specifying such parameters may lead to extremely low-powered tests. Here we develop highly adaptive tests to detect group differences in brain connectivity while accounting for unknown optimal choices of some tuning parameters. The proposed tests combine statistical evidence against a null hypothesis from multiple sources across a range of plausible tuning parameter values reflecting uncertainty with the unknown truth. These highly adaptive tests are not only

  10. Highly adaptive tests for group differences in brain functional connectivity

    PubMed Central

    Kim, Junghi; Pan, Wei

    2015-01-01

    Resting-state functional magnetic resonance imaging (rs-fMRI) and other technologies have been offering evidence and insights showing that altered brain functional networks are associated with neurological illnesses such as Alzheimer's disease. Exploring brain networks of clinical populations compared to those of controls would be a key inquiry to reveal underlying neurological processes related to such illnesses. For such a purpose, group-level inference is a necessary first step in order to establish whether there are any genuinely disrupted brain subnetworks. Such an analysis is also challenging due to the high dimensionality of the parameters in a network model and high noise levels in neuroimaging data. We are still in the early stage of method development as highlighted by Varoquaux and Craddock (2013) that “there is currently no unique solution, but a spectrum of related methods and analytical strategies” to learn and compare brain connectivity. In practice the important issue of how to choose several critical parameters in estimating a network, such as what association measure to use and what is the sparsity of the estimated network, has not been carefully addressed, largely because the answers are unknown yet. For example, even though the choice of tuning parameters in model estimation has been extensively discussed in the literature, as to be shown here, an optimal choice of a parameter for network estimation may not be optimal in the current context of hypothesis testing. Arbitrarily choosing or mis-specifying such parameters may lead to extremely low-powered tests. Here we develop highly adaptive tests to detect group differences in brain connectivity while accounting for unknown optimal choices of some tuning parameters. The proposed tests combine statistical evidence against a null hypothesis from multiple sources across a range of plausible tuning parameter values reflecting uncertainty with the unknown truth. These highly adaptive tests are not

  11. Localization and attempted quantification of various functional groups on pulpwood fibres

    NASA Astrophysics Data System (ADS)

    Klash, A.; Ncube, E.; Meincken, M.

    2009-04-01

    The distribution of different free chemical functional groups on wood and pulp fibres has been determined by means of atomic force microscopy (AFM) with chemically modified tips. Because these functional groups show a higher affinity to similar groups on the substrate surface during scanning, AFM images determined with an additional digital pulsed-force mode (DPFM) controller allow the distribution of the chemical components to be imaged and to a degree also to be quantified. The investigated tip coatings showed a different sensitivity towards the major chemical components present in wood fibres, determined on spin-coated films and on wood fibres. A clear distinction between cellulose and lignin was possible in both cases. This technique could therefore be used to differentiate between cellulose and lignin present on pulp fibre surfaces and confirm the successful removal of lignin by pulping.

  12. Social skills group training in high-functioning autism: A qualitative responder study.

    PubMed

    Choque Olsson, Nora; Rautio, Daniel; Asztalos, Jenny; Stoetzer, Ulrich; Bölte, Sven

    2016-11-01

    Systematic reviews show some evidence for the efficacy of group-based social skills group training in children and adolescents with autism spectrum disorder, but more rigorous research is needed to endorse generalizability. In addition, little is known about the perspectives of autistic individuals participating in social skills group training. Using a qualitative approach, the objective of this study was to examine experiences and opinions about social skills group training of children and adolescents with higher functioning autism spectrum disorder and their parents following participation in a manualized social skills group training ("KONTAKT"). Within an ongoing randomized controlled clinical trial (NCT01854346) and based on outcome data from the Social Responsiveness Scale, six high responders and five low-to-non-responders to social skills group training and one parent of each child (N = 22) were deep interviewed. Interestingly, both high responders and low-to-non-responders (and their parents) reported improvements in social communication and related skills (e.g. awareness of own difficulties, self-confidence, independence in everyday life) and overall treatment satisfaction, although more positive intervention experiences were expressed by responders. These findings highlight the added value of collecting verbal data in addition to quantitative data in a comprehensive evaluation of social skills group training.

  13. Functional network organizations of two contrasting temperament groups in dimensions of novelty seeking and harm avoidance.

    PubMed

    Kyeong, Sunghyon; Kim, Eunjoo; Park, Hae-Jeong; Hwang, Dong-Uk

    2014-08-05

    Novelty seeking (NS) and harm avoidance (HA) are two major dimensions of temperament in Cloninger׳s neurobiological model of personality. Previous neurofunctional and biological studies on temperament dimensions of HA and NS suggested that the temperamental traits have significant correlations with cortical and subcortical brain regions. However, no study to date has investigated the functional network modular organization as a function of the temperament dimension. The temperament dimensions were originally proposed to be independent of one another. However, a meta-analysis based on 16 published articles found a significant negative correlation between HA and NS (Miettunen et al., 2008). Based on this negative correlation, the current study revealed the whole-brain connectivity modular architecture for two contrasting temperament groups. The k-means clustering algorithm, with the temperamental traits of HA and NS as an input, was applied to divide the 40 subjects into two temperament groups: 'high HA and low NS' versus 'low HA and high NS'. Using the graph theoretical framework, we found a functional segregation of whole brain network architectures derived from resting-state functional MRI. In the 'high HA and low NS' group, the regulatory brain regions, such as the prefrontal cortex (PFC), are clustered together with the limbic system. In the 'low HA and high NS' group, however, brain regions lying on the dopaminergic pathways, such as the PFC and basal ganglia, are partitioned together. These findings suggest that the neural basis of inhibited, passive, and inactive behaviors in the 'high HA and low NS' group was derived from the increased network associations between the PFC and limbic clusters. In addition, supporting evidence of topological differences between the two temperament groups was found by analyzing the functional connectivity density and gray matter volume, and by computing the relationships between the morphometry and function of the brain.

  14. Brief Report: Additive and Subtractive Counterfactual Reasoning of Children with High-Functioning Autism Spectrum Disorders

    ERIC Educational Resources Information Center

    Begeer, Sander; Terwogt, Mark Meerum; Lunenburg, Patty; Stegge, Hedy

    2009-01-01

    The development of additive ("If only I had done...") and subtractive ("If only I had not done....") counterfactual reasoning was examined in children with High Functioning Autism Spectrum Disorders (HFASD) (n = 72) and typically developing controls (n = 71), aged 6-12 years. Children were presented four stories where they could generate…

  15. Robust estimation of mean and dispersion functions in extended generalized additive models.

    PubMed

    Croux, Christophe; Gijbels, Irène; Prosdocimi, Ilaria

    2012-03-01

    Generalized linear models are a widely used method to obtain parametric estimates for the mean function. They have been further extended to allow the relationship between the mean function and the covariates to be more flexible via generalized additive models. However, the fixed variance structure can in many cases be too restrictive. The extended quasilikelihood (EQL) framework allows for estimation of both the mean and the dispersion/variance as functions of covariates. As for other maximum likelihood methods though, EQL estimates are not resistant to outliers: we need methods to obtain robust estimates for both the mean and the dispersion function. In this article, we obtain functional estimates for the mean and the dispersion that are both robust and smooth. The performance of the proposed method is illustrated via a simulation study and some real data examples.

  16. 14 CFR Section 11 - Functional Classification-Operating Expenses of Group II and Group III Air Carriers

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Functional Classification-Operating... ACCOUNTS AND REPORTS FOR LARGE CERTIFICATED AIR CARRIERS Profit and Loss Classification Section 11 Functional Classification—Operating Expenses of Group II and Group III Air Carriers 5100Flying Operations....

  17. Functional trait responses to grazing are mediated by soil moisture and plant functional group identity

    PubMed Central

    Zheng, Shuxia; Li, Wenhuai; Lan, Zhichun; Ren, Haiyan; Wang, Kaibo

    2015-01-01

    Abundant evidence has shown that grazing alters plant functional traits, community structure and ecosystem functioning of grasslands. Few studies, however, have tested how plant responses to grazing are mediated by resource availability and plant functional group identity. We examined the effects of grazing on functional traits across a broad range of species along a soil moisture gradient in Inner Mongolia grassland. Our results showed that trait syndromes of plant size (individual biomass) and shoot growth (leaf N content and leaf density) distinguished plant species responses to grazing. The effects of grazing on functional traits were mediated by soil moisture and dependent on functional group identity. For most species, grazing decreased plant height but increased leaf N and specific leaf area (SLA) along the moisture gradient. Grazing enhanced the community-weighted attributes (leaf NCWM and SLACWM), which were triggered mainly by the positive trait responses of annuals and biennials and perennial grasses, and increased relative abundance of perennial forbs. Our results suggest that grazing-induced species turnover and increased intraspecific trait variability are two drivers for the observed changes in community weighted attributes. The dominant perennial bunchgrasses exhibited mixed tolerance–resistance strategies to grazing and mixed acquisitive–conservative strategies in resource utilization. PMID:26655858

  18. Dental indications for the instrumental functional analysis in additional consideration of health-economic aspects

    PubMed Central

    Tinnemann, Peter; Stöber, Yvonne; Roll, Stephanie; Vauth, Christoph; Willich, Stefan N.; Greiner, Wolfgang

    2010-01-01

    Background Besides clinical and radiological examination instrumental functional analyses are performed as diagnostic procedures for craniomandibular dysfunctions. Instrumental functional analyses cause substantial costs and shows a considerable variability between individual dentist practices. Objectives On the basis of published scientific evidence the validity of the instrumental functional analysis for the diagnosis of craniomandibular dysfunctions compared to clinical diagnostic procedures; the difference of the various forms of the instrumental functional analysis; the existence of a dependency on additional other factors and the need for further research are determined in this report. In addition, the cost effectiveness of the instrumental functional analysis is analysed in a health-policy context, and social, legal and ethical aspects are considered. Methods A literature search is performed in over 27 databases and by hand. Relevant companies and institutions are contacted concerning unpublished studies. The inclusion criteria for publications are (i) diagnostic studies with the indication “craniomandibular malfunction”, (ii) a comparison between clinical and instrumental functional analysis, (iii) publications since 1990, (iv) publications in English or German. The identified literature is evaluated by two scientists regarding the relevance of content and methodical quality. Results The systematic database search resulted in 962 hits. 187 medical and economic complete publications are evaluated. Since the evaluated studies are not relevant enough to answer the medical or health economic questions no study is included. Discussion The inconsistent terminology concerning craniomandibular dysfunctions and instrumental functional analyses results in a broad literature search in databases and an extensive search by hand. Since no relevant results concerning the validity of the instrumental functional analysis in comparison to the clinical functional analysis

  19. Ecosystem functions and densities of contributing functional groups respond in a different way to chemical stress.

    PubMed

    De Laender, Frederik; Taub, Frieda B; Janssen, Colin R

    2011-12-01

    Understanding whether and to what extent ecosystem functions respond to chemicals is a major challenge in environmental toxicology. The available data gathered by ecosystem-level experiments (micro- and mesocosms) often describe the responses of taxa densities to stress. However, whether these responses are proportional to the responses of associated ecosystem functions to stress is unclear. By combining a carbon budget modeling technique with data from a standardized microcosm experiment with a known community composition, we quantified three ecosystem functions (net primary production [NPP], net mesozooplankton production [NZP], and net bacterial production [NBP]) at three Cu concentrations, with a control. Changes of these ecosystem functions with increasing chemical concentrations were not always proportional to the Cu effects on the densities of the contributing functional groups. For example, Cu treatments decreased mesozooplankton density by 100-fold and increased phytoplankton density 10- to 100-fold while increasing NZP and leaving NPP unaltered. However, in contrast, Cu affected microzooplankton and the associated function (NBP) in a comparable way. We illustrate that differences in the response of phytoplankton/mesozooplankton densities and the associated ecosystem functions to stress occur because functional rates (e.g., photosynthesis rates/ingestion rates) vary among Cu treatments and in time. These variations could be explained by food web ecology but not by direct Cu effects, indicating that ecology may be a useful basis for understanding environmental effects of stressors.

  20. Group additive values for the gas-phase standard enthalpy of formation, entropy and heat capacity of oxygenates.

    PubMed

    Paraskevas, Paschalis D; Sabbe, Maarten K; Reyniers, Marie-Françoise; Papayannakos, Nikos; Marin, Guy B

    2013-11-25

    A complete and consistent set of 60 Benson group additive values (GAVs) for oxygenate molecules and 97 GAVs for oxygenate radicals is provided, which allow to describe their standard enthalpies of formation, entropies and heat capacities. Approximately half of the GAVs for oxygenate molecules and the majority of the GAVs for oxygenate radicals have not been reported before. The values are derived from an extensive and accurate database of thermochemical data obtained by ab initio calculations at the CBS-QB3 level of theory for 202 molecules and 248 radicals. These compounds include saturated and unsaturated, α- and β-branched, mono- and bifunctional oxygenates. Internal rotations were accounted for by using one-dimensional hindered rotor corrections. The accuracy of the database was further improved by adding bond additive corrections to the CBS-QB3 standard enthalpies of formation. Furthermore, 14 corrections for non-nearest-neighbor interactions (NNI) were introduced for molecules and 12 for radicals. The validity of the constructed group additive model was established by comparing the predicted values with both ab initio calculated values and experimental data for oxygenates and oxygenate radicals. The group additive method predicts standard enthalpies of formation, entropies, and heat capacities with chemical accuracy, respectively, within 4 kJ mol(-1) and 4 J mol(-1) K(-1) for both ab initio calculated and experimental values. As an alternative, the hydrogen bond increment (HBI) method developed by Lay et al. (T. H. Lay, J. W. Bozzelli, A. M. Dean, E. R. Ritter, J. Phys. Chem.- 1995, 99, 14514) was used to introduce 77 new HBI structures and to calculate their thermodynamic parameters (Δ(f)H°, S°, C(p)°). The GAVs reported in this work can be reliably used for the prediction of thermochemical data for large oxygenate compounds, combining rapid prediction with wide-ranging application.

  1. Plant Species and Functional Group Combinations Affect Green Roof Ecosystem Functions

    PubMed Central

    Lundholm, Jeremy; MacIvor, J. Scott; MacDougall, Zachary; Ranalli, Melissa

    2010-01-01

    Background Green roofs perform ecosystem services such as summer roof temperature reduction and stormwater capture that directly contribute to lower building energy use and potential economic savings. These services are in turn related to ecosystem functions performed by the vegetation layer such as radiation reflection and transpiration, but little work has examined the role of plant species composition and diversity in improving these functions. Methodology/Principal Findings We used a replicated modular extensive (shallow growing- medium) green roof system planted with monocultures or mixtures containing one, three or five life-forms, to quantify two ecosystem services: summer roof cooling and water capture. We also measured the related ecosystem properties/processes of albedo, evapotranspiration, and the mean and temporal variability of aboveground biomass over four months. Mixtures containing three or five life-form groups, simultaneously optimized several green roof ecosystem functions, outperforming monocultures and single life-form groups, but there was much variation in performance depending on which life-forms were present in the three life-form mixtures. Some mixtures outperformed the best monocultures for water capture, evapotranspiration, and an index combining both water capture and temperature reductions. Combinations of tall forbs, grasses and succulents simultaneously optimized a range of ecosystem performance measures, thus the main benefit of including all three groups was not to maximize any single process but to perform a variety of functions well. Conclusions/Significance Ecosystem services from green roofs can be improved by planting certain life-form groups in combination, directly contributing to climate change mitigation and adaptation strategies. The strong performance by certain mixtures of life-forms, especially tall forbs, grasses and succulents, warrants further investigation into niche complementarity or facilitation as mechanisms

  2. Group additivity values for estimating the enthalpy of formation of organic compounds: an update and reappraisal. 2. C, H, N, O, S, and halogens.

    PubMed

    Holmes, John L; Aubry, Christiane

    2012-07-05

    This study extends a previous publication on group additivity values (GAVs) for the elements C, H, and O, to include the elements nitrogen, sulfur, and the halogens. The present state and utility of the Benson additivity schemes for estimating the enthalpy of formation (Δ(f)H(0)) of organic compounds are again described, extending them to include more elements. Old and new GAVs for a wide variety of compounds are provided and are revised where necessary. When new terms are proposed, or old ones are significantly altered, the rationale for so doing is presented. GAV derived ring strain values for benzene and pyridine indicate that the aromatic stabilization of each is essentially the same. As before, the thermochemical consequences of replacing one functional group by another are also shown, thus permitting quick shortcuts to the estimation of new Δ(f)H(0) values.

  3. Effects of benthos on sediment transport: difficulties with functional grouping

    NASA Astrophysics Data System (ADS)

    Jumars, P. A.; Nowell, A. R. M.

    No consistent functional grouping of organisms as stabilizers vs destabilizers, respectively decreasing or enhancing erodibility, is possible. Benthic organisms can affect erodibility in particular—and sediment transport in general—via alternation (1) of fluid momentum impinging on the bed, (2) of particle exposure to the flow, (3) of adhesion between particles, and (4) of particle momentum. The net effects of a species or individual on erosion and deposition thresholds or on transport rates are not in general predictable from extant data. Furthermore, they depend upon the context of flow conditions, bed configuration, and community composition into which the organism is set. Separation of organism effects into these four categories does, however, allow their explicit incorporation into DuBoys-type and stochastic sediment dynamic models already in use and thus permits the specification of parameters whose measurement will enhance predictability of sediment transport modes and rates in natural, organism-influenced, marine settings. If the variable of prime concern is the total amount of sediment transported, rather than the frequency of transport events or the spatial pattern of erosion and eposition, and if most transport occurs in rare but intense bouts (e.g., winter storms on boreal continental shelves), then it may be possible to ignore organism effects without major sacrifices in accuracy or precision. Under high transport rates, suspended load effects override organism-produced bottom roughness, abrasion removes adhesives from transporting grains, and transport rates (normalized per unit width of the channel or bed) exceed feeding and pelletization rates. Moreover, at high rates most material transports as suspended load, effectively out of reach of the benthos. The transport rates at which organism effects are overridden, however, remain to be determined. For lower transport rates, foraging theory promises to provide insights into organism effects.

  4. METALLICITY DISTRIBUTION FUNCTIONS OF FOUR LOCAL GROUP DWARF GALAXIES

    SciTech Connect

    Ross, Teresa L.; Holtzman, Jon; Saha, Abhijit; Anthony-Twarog, Barbara J. E-mail: holtz@nmsu.edu

    2015-06-15

    We present stellar metallicities in Leo I, Leo II, IC 1613, and Phoenix dwarf galaxies derived from medium (F390M) and broad (F555W, F814W) band photometry using the Wide Field Camera 3 instrument on board the Hubble Space Telescope. We measured metallicity distribution functions (MDFs) in two ways, (1) matching stars to isochrones in color–color diagrams and (2) solving for the best linear combination of synthetic populations to match the observed color–color diagram. The synthetic technique reduces the effect of photometric scatter and produces MDFs 30%–50% narrower than the MDFs produced from individually matched stars. We fit the synthetic and individual MDFs to analytical chemical evolution models (CEMs) to quantify the enrichment and the effect of gas flows within the galaxies. Additionally, we measure stellar metallicity gradients in Leo I and II. For IC 1613 and Phoenix our data do not have the radial extent to confirm a metallicity gradient for either galaxy. We find the MDF of Leo I (dwarf spheroidal) to be very peaked with a steep metal-rich cutoff and an extended metal-poor tail, while Leo II (dwarf spheroidal), Phoenix (dwarf transition), and IC 1613 (dwarf irregular) have wider, less peaked MDFs than Leo I. A simple CEM is not the best fit for any of our galaxies; therefore we also fit the “Best Accretion Model” of Lynden-Bell. For Leo II, IC 1613, and Phoenix we find similar accretion parameters for the CEM even though they all have different effective yields, masses, star formation histories, and morphologies. We suggest that the dynamical history of a galaxy is reflected in the MDF, where broad MDFs are seen in galaxies that have chemically evolved in relative isolation and narrowly peaked MDFs are seen in galaxies that have experienced more complicated dynamical interactions concurrent with their chemical evolution.

  5. Students' Perceptions of Classroom Group Work as a Function of Group Member Selection

    ERIC Educational Resources Information Center

    Myers, Scott A.

    2012-01-01

    The purpose of this assessment was to examine whether differences exist between students who self-select their classroom work group members and students who are randomly assigned to their classroom work groups in terms of their use of organizational citizenship behaviors with their work group members; their commitment to, trust in, and relational…

  6. The Use of Additive Manufacturing for Fabrication of Multi-Function Small Satellite Structures

    SciTech Connect

    Horais, Brian J; Love, Lonnie J; Dehoff, Ryan R

    2013-01-01

    The use of small satellites in constellations is limited only by the growing functionality of smallsats themselves. Additive manufacturing provides exciting new design opportunities for development of multifunction CubeSat structures that integrate such functions as propulsion and thermal control into the satellite structures themselves. Manufacturing of these complex multifunction structures is now possible in lightweight, high strength, materials such as titanium by using existing electron beam melting additive manufacturing processes. However, the use of today's additive manufacturing capabilities is often cost-prohibitive for small companies due to the large capital investments required. To alleviate this impediment the U.S. Department of Energy has established a Manufacturing Demonstration Facility (MDF) at their Oak Ridge National Laboratory (ORNL) in Tennessee that provides industry access to a broad range of energy-efficient additive manufacturing equipment for collaborative use by both small and large organizations. This paper presents a notional CubeSat multifunction design that integrates the propulsion system into a three-unit (3U) CubeSat structure. The full-scale structure has been designed and fabricated at the ORNL MDF. The use of additive manufacturing for spacecraft fabrication is opening up many new possibilities in design and fabrication capabilities for what had previously been impossible structures to fabricate.

  7. A SPARSE REDUCED RANK FRAMEWORK FOR GROUP ANALYSIS OF FUNCTIONAL NEUROIMAGING DATA.

    PubMed

    Ahn, Mihye; Shen, Haipeng; Lin, Weili; Zhu, Hongtu

    2015-01-01

    In spatial-temporal neuroimaging studies, there is an evolving literature on the analysis of functional imaging data in order to learn the intrinsic functional connectivity patterns among different brain regions. However, there are only few efficient approaches for integrating functional connectivity pattern across subjects, while accounting for spatial-temporal functional variation across multiple groups of subjects. The objective of this paper is to develop a new sparse reduced rank (SRR) modeling framework for carrying out functional connectivity analysis across multiple groups of subjects in the frequency domain. Our new framework not only can extract both frequency and spatial factors across subjects, but also imposes sparse constraints on the frequency factors. It thus leads to the identification of important frequencies with high power spectra. In addition, we propose two novel adaptive criteria for automatic selection of sparsity level and model rank. Using simulated data, we demonstrate that SRR outperforms several existing methods. Finally, we apply SRR to detect group differences between controls and two subtypes of attention deficit hyperactivity disorder (ADHD) patients, through analyzing the ADHD-200 data.

  8. Red electroluminescence of ruthenium sensitizer functionalized by sulfonate anchoring groups.

    PubMed

    Shahroosvand, Hashem; Abbasi, Parisa; Mohajerani, Ezeddin; Janghouri, Mohammad

    2014-06-28

    We have synthesized five novel Ru(ii) phenanthroline complexes with an additional aryl sulfonate ligating substituent at the 5-position [Ru(L)(bpy)2](BF4)2 (1), [Ru(L)(bpy)(SCN)2] (2), [Ru(L)3](BF4)2 (3), [Ru(L)2(bpy)](BF4)2 (4) and [Ru(L)(BPhen)(SCN)2] (5) (where L = 6-one-[1,10]phenanthroline-5-ylamino)-3-hydroxynaphthalene 1-sulfonic, bpy = 2,2'-bipyridine, BPhen = 4,7-diphenyl-1,10-phenanthroline), as both photosensitizers for oxide semiconductor solar cells (DSSCs) and light emitting diodes (LEDs). The absorption and emission maxima of these complexes red shifted upon extending the conjugation of the phenanthroline ligand. Ru phenanthroline complexes exhibit broad metal to ligand charge transfer-centered electroluminescence (EL) with a maximum near 580 nm. Our results indicated that a particular structure (2) can be considered as both DSSC and OLED devices. The efficiency of the LED performance can be tuned by using a range of ligands. Device (2) has a luminance of 550 cd m(-2) and maximum efficiency of 0.9 cd A(-1) at 18 V, which are the highest values among the five devices. The turn-on voltage of this device is approximately 5 V. The role of auxiliary ligands in the photophysical properties of Ru complexes was investigated by DFT calculation. We have also studied photovoltaic properties of dye-sensitized nanocrystalline semiconductor solar cells based on Ru phenanthroline complexes and an iodine redox electrolyte. A solar energy to electricity conversion efficiency (η) of 0.67% was obtained for Ru complex (2) under standard AM 1.5 irradiation with a short-circuit photocurrent density (Jsc) of 2.46 mA cm(-2), an open-circuit photovoltage (Voc) of 0.6 V, and a fill factor (ff) of 40%, which are all among the highest values for ruthenium sulfonated anchoring groups reported so far. Monochromatic incident photon to current conversion efficiency was 23% at 475 nm. Photovoltaic studies clearly indicated dyes with two SCN substituents yielded a higher Jsc for the

  9. Coumestan inhibits radical-induced oxidation of DNA: is hydroxyl a necessary functional group?

    PubMed

    Xi, Gao-Lei; Liu, Zai-Qun

    2014-06-18

    Coumestan is a natural tetracycle with a C═C bond shared by a coumarin moiety and a benzofuran moiety. In addition to the function of the hydroxyl group on the antioxidant activity of coumestan, it is worth exploring the influence of the oxygen-abundant scaffold on the antioxidant activity as well. In this work, seven coumestans containing electron-withdrawing and electron-donating groups were synthesized to evaluate the abilities to trap 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonate) cationic radical (ABTS(•+)), 2,2'-diphenyl-1-picrylhydrazyl radical (DPPH), and galvinoxyl radical, respectively, and to inhibit the oxidations of DNA mediated by (•)OH, Cu(2+)/glutathione (GSH), and 2,2'-azobis(2-amidinopropane hydrochloride) (AAPH), respectively. It was found that all of the coumestans used herein can quench the aforementioned radicals and can inhibit (•)OH-, Cu(2+)/GSH-, and AAPH-induced oxidations of DNA. In particular, substituent-free coumestan exhibits higher ability to quench DPPH and to inhibit AAPH-induced oxidation of DNA than Trolox. In addition, nonsubstituted coumestan shows a similar ability to inhibit (•)OH- and Cu(2+)/GSH-induced oxidations of DNA relative to that of Trolox. The antioxidant effectiveness of the coumestan can be attributed to the lactone in the coumarin moiety and, therefore, a hydroxyl group may not be a necessary functional group for coumestan to be an antioxidant.

  10. Metallicity Distribution Functions of Four Local Group Dwarf Galaxies

    NASA Astrophysics Data System (ADS)

    Ross, Teresa L.; Holtzman, Jon; Saha, Abhijit; Anthony-Twarog, Barbara J.

    2015-06-01

    We present stellar metallicities in Leo I, Leo II, IC 1613, and Phoenix dwarf galaxies derived from medium (F390M) and broad (F555W, F814W) band photometry using the Wide Field Camera 3 instrument on board the Hubble Space Telescope. We measured metallicity distribution functions (MDFs) in two ways, (1) matching stars to isochrones in color-color diagrams and (2) solving for the best linear combination of synthetic populations to match the observed color-color diagram. The synthetic technique reduces the effect of photometric scatter and produces MDFs 30%-50% narrower than the MDFs produced from individually matched stars. We fit the synthetic and individual MDFs to analytical chemical evolution models (CEMs) to quantify the enrichment and the effect of gas flows within the galaxies. Additionally, we measure stellar metallicity gradients in Leo I and II. For IC 1613 and Phoenix our data do not have the radial extent to confirm a metallicity gradient for either galaxy. We find the MDF of Leo I (dwarf spheroidal) to be very peaked with a steep metal-rich cutoff and an extended metal-poor tail, while Leo II (dwarf spheroidal), Phoenix (dwarf transition), and IC 1613 (dwarf irregular) have wider, less peaked MDFs than Leo I. A simple CEM is not the best fit for any of our galaxies; therefore we also fit the “Best Accretion Model” of Lynden-Bell. For Leo II, IC 1613, and Phoenix we find similar accretion parameters for the CEM even though they all have different effective yields, masses, star formation histories, and morphologies. We suggest that the dynamical history of a galaxy is reflected in the MDF, where broad MDFs are seen in galaxies that have chemically evolved in relative isolation and narrowly peaked MDFs are seen in galaxies that have experienced more complicated dynamical interactions concurrent with their chemical evolution. Based on observations made with the NASA/ESA Hubble Space Telescope, obtained at the Space Telescope Science Institute, which is

  11. Moral Judgment as a Function of Peer Group Interaction

    ERIC Educational Resources Information Center

    Maitland, Karen A.; Goldman, Jacquelin R.

    1974-01-01

    This article presents an investigation into the effects of peer group interaction on moral judgment among 36 male and female eleventh and twelfth graders. The results indicate greater social conflict and pressure in a group discussion induces greater change in the level of moral judgment. (DE)

  12. Perceptual Visual Grouping under Inattention: Electrophysiological Functional Imaging

    ERIC Educational Resources Information Center

    Razpurker-Apfeld, Irene; Pratt, Hillel

    2008-01-01

    Two types of perceptual visual grouping, differing in complexity of shape formation, were examined under inattention. Fourteen participants performed a similarity judgment task concerning two successive briefly presented central targets surrounded by task-irrelevant simple and complex grouping patterns. Event-related potentials (ERPs) were…

  13. Compositions, Functions, and Testing of Friction Brake Materials and Their Additives

    SciTech Connect

    Blau, PJ

    2001-10-22

    The purpose of this report is to present a survey of commercial brake materials and additives, and to indicate their typical properties and functions, especially as regards their use in heavy trucks. Most truck pad and shoe materials described here were designed to wear against cast iron. Brake material test methods are also briefly described. This report does not address issues associated with the fabrication and manufacturing of brake materials. Since there are literally thousands of brake material additives, and their combinations are nearly limitless, it is impractical to list them all here. Rather, an attempt has been made to capture the primary constituents and their functions. An Appendix contains thermo-physical properties of some current and potential brake materials.

  14. Radial distribution functions of non-additive hard sphere mixtures via Percus' test particle route.

    PubMed

    Hopkins, Paul; Schmidt, Matthias

    2011-08-17

    Using fundamental density functional theory we calculate the partial radial distribution functions, g(ij)(r), of a binary non-additive hard sphere mixture using either Percus' test particle approach or inversion of the analytic structure factor obtained via the Ornstein-Zernike route. We find good agreement between the theoretical results and Monte Carlo simulation data for both positive and moderate negative non-additivities. We investigate the asymptotic, [Formula: see text], decay of the g(ij)(r) and show that this agrees with the analytic analysis of the contributions to the partial structure factors in the plane of complex wavevectors. We find the test particle density profiles to be free of unphysical artefacts, contrary to earlier reports.

  15. Dominant Functional Group Effects on the Invasion Resistance at Different Resource Levels

    PubMed Central

    Wang, Jiang; Ge, Yuan; Zhang, Chong B.; Bai, Yi; Du, Zhao K.

    2013-01-01

    Background Functional group composition may affect invasion in two ways the effect of abundance, i.e. dominance of functional group; and the effect of traits, i.e. identity of functional groups. However, few studies have focused on the role of abundance of functional group on invasion resistance. Moreover, how resource availability influences the role of the dominant functional group in invasion resistance is even less understood. Methodology/Principal Findings In this experiment, we established experimental pots using four different functional groups (annual grass, perennial grass, deciduous shrub or arbor and evergreen shrub or arbor), and the dominant functional group was manipulated. These experimental pots were respectively constructed at different soil nitrogen levels (control and fertilized). After one year of growth, we added seeds of 20 different species (five species per functional group) to the experimental pots. Fertilization significantly increased the overall invasion success, while dominant functional group had little effect on overall invasion success. When invaders were grouped into functional groups, invaders generally had lower success in pots dominated by the same functional group in the control pots. However, individual invaders of the same functional group exhibited different invasion patterns. Fertilization generally increased success of invaders in pots dominated by the same than by another functional group. However, fertilization led to great differences for individual invaders. Conclusions/Significance The results showed that the dominant functional group, independent of functional group identity, had a significant effect on the composition of invaders. We suggest that the limiting similarity hypothesis may be applicable at the functional group level, and limiting similarity may have a limited role for individual invaders as shown by the inconsistent effects of dominant functional group and fertilization. PMID:24167565

  16. Risk assessment of nitrate and oxytetracycline addition on coastal ecosystem functions.

    PubMed

    Feng-Jiao, Liu; Shun-Xing, Li; Feng-Ying, Zheng; Xu-Guang, Huang; Yue-Gang, Zuo; Teng-Xiu, Tu; Xue-Qing, Wu

    2014-01-01

    Diatoms dominate phytoplankton communities in the well-mixed coastal and upwelling regions. Coastal diatoms are often exposed to both aquaculture pollution and eutrophication. But how these exposures influence on coastal ecosystem functions are unknown. To examine these influences, a coastal centric diatom, Conticribra weissflogii was maintained at different concentrations of nitrate (N) and/or oxytetracycline (OTC). Algal density, cell growth cycle, protein, chlorophyll a, superoxide dismutase (SOD) activity, and malonaldehyde (MDA) were determined for the assessment of algal biomass, lifetime, nutritional value, photosynthesis and respiration, antioxidant capacity, and lipid peroxidation, respectively. When N addition was combined with OTC pollution, the cell growth cycles were shortened by 56-73%; algal density, SOD activities, the concentrations of chlorophyll a, protein, and MDA varied between 73 and 121%, 19 and 397%, 52 and 693%, 19 and 875%, and 66 and 2733% of the values observed in N addition experiments, respectively. According to P-value analysis, the influence of OTC on algal density and SOD activity was not significant, but the effect on cell growth cycle, protein, chlorophyll a, and MDA were significant (P<0.05). The influence of N addition with simultaneous OTC pollution on the above six end points was significant. Algal biomass, lifetime, nutrition, antioxidant capacity, lipid peroxidation, photosynthesis, and respiration were all affected by the addition of OTC and N. Coastal ecosystem functions were severely affected by N and OTC additions, and the influence was increased in the order: Nfunctions.

  17. Alumina Matrix Composites with Non-Oxide Nanoparticle Addition and Enhanced Functionalities

    PubMed Central

    Galusek, Dušan; Galusková, Dagmar

    2015-01-01

    The addition of SiC or TiC nanoparticles to polycrystalline alumina matrix has long been known as an efficient way of improving the mechanical properties of alumina-based ceramics, especially strength, creep, and wear resistance. Recently, new types of nano-additives, such as carbon nanotubes (CNT), carbon nanofibers (CNF), and graphene sheets have been studied in order not only to improve the mechanical properties, but also to prepare materials with added functionalities, such as thermal and electrical conductivity. This paper provides a concise review of several types of alumina-based nanocomposites, evaluating the efficiency of various preparation methods and additives in terms of their influence on the properties of composites.

  18. Changes in composition and abundance of functional groups of arctic fungi in response to long-term summer warming

    PubMed Central

    Semenova, Tatiana A.; Morgado, Luis N.; Welker, Jeffrey M.

    2016-01-01

    We characterized fungal communities in dry and moist tundra and investigated the effect of long-term experimental summer warming on three aspects of functional groups of arctic fungi: richness, community composition and species abundance. Warming had profound effects on community composition, abundance, and, to a lesser extent, on richness of fungal functional groups. In addition, our data show that even within functional groups, the direction and extent of response to warming tend to be species-specific and we recommend that studies on fungal communities and their roles in nutrient cycling take into account species-level responses. PMID:27881760

  19. Organic Mass Fragments and Organic Functional Groups in Aged Biomass Burning and Fossil Fuel Combustion Aerosol

    NASA Astrophysics Data System (ADS)

    Day, D. A.; Hawkins, L. N.; Russell, L. M.

    2009-12-01

    Organic functional group concentrations in submicron aerosol particles collected from 27 June to 17 September at the Scripps Pier in La Jolla, California as part of AeroSCOPE 2008 were quantified using Fourier Transform Infrared (FTIR) spectroscopy. Organic and inorganic non-refractory components in the same air masses were quantified using a Quadrupole Aerosol Mass Spectrometer (Q-AMS). Previous measurements at the Scripps pier indicate that a large fraction of submicron particle mass originates in Los Angeles and the port of Long Beach. Additional particle sources to the region include local urban emissions and periodic biomass burning during large wildfires. Three distinct types of organic aerosol components were identified from organic composition and elemental tracers, including biomass burning, fossil fuel combustion, and polluted marine components. Fossil fuel combustion organic aerosol was dominated by unsaturated alkane and was correlated with sulfur, vanadium, and nickel supporting ship and large trucks in and around the Los Angeles/Long Beach region as the dominant source. Biomass burning organic aerosol comprised a smaller unsaturated alkane fraction and larger fractions of non-acid carbonyl, amine, and carboxylic acid and was correlated with potassium and bromine. Polluted marine organic aerosol was dominated by organic hydroxyl and unsaturated alkane and was not correlated with any elemental tracers. Mass spectra of the organic aerosol support the aerosol sources determined by organic functional groups and elemental tracers and contain fragments commonly attributed to oxygenated organic aerosol (OOA), hydrocarbon-like organic aerosol (HOA), and biomass burning organic aerosol (BBOA). Comparisons of the PMF-derived Q-AMS source spectra with FTIR source spectra and functional group composition provide additional information on the relationship between commonly reported organic aerosol factors and organic functional groups in specific organic aerosol

  20. The central role of ketones in reversible and irreversible hydrothermal organic functional group transformations

    NASA Astrophysics Data System (ADS)

    Yang, Ziming; Gould, Ian R.; Williams, Lynda B.; Hartnett, Hilairy E.; Shock, Everett L.

    2012-12-01

    Studies of hydrothermal reactions involving organic compounds suggest complex, possibly reversible, reaction pathways that link functional groups from reduced alkanes all the way to oxidized carboxylic acids. Ketones represent a critical functional group because they occupy a central position in the reaction pathway, at the point where Csbnd C bond cleavage is required for the formation of the more oxidized carboxylic acids. The mechanisms for the critical bond cleavage reactions in ketones, and how they compete with other reactions are the focus of this experimental study. We studied a model ketone, dibenzylketone (DBK), in H2O at 300 °C and 70 MPa for up to 528 h. Product analysis was performed as a function of time at low DBK conversions to reveal the primary reaction pathways. Reversible interconversion between ketone, alcohol, alkene and alkane functional groups is observed in addition to formation of radical coupling products derived from irreversible Csbnd C and Csbnd H homolytic bond cleavage. The product distributions are time-dependent but the bond cleavage products dominate. The major products that accumulate at longer reaction times are toluene and larger, dehydrogenated structures that are initially formed by radical coupling. The hydrogen atoms generated by dehydrogenation of the coupling products are predominantly consumed in the formation of toluene. Even though bond cleavage products dominate, no carboxylic acids were observed on the timescale of the reactions under the chosen experimental conditions.

  1. Cobalt(III)-Catalyzed Synthesis of Indazoles and Furans by C–H Bond Functionalization/Addition/Cyclization Cascades

    PubMed Central

    2015-01-01

    The development of operationally straightforward and cost-effective routes for the assembly of heterocycles from simple inputs is important for many scientific endeavors, including pharmaceutical, agrochemical, and materials research. In this article we describe the development of a new air-stable cationic Co(III) catalyst for convergent, one-step benchtop syntheses of N-aryl-2H-indazoles and furans by C–H bond additions to aldehydes followed by in situ cyclization and aromatization. Only a substoichiometric amount of AcOH is required as an additive that is both low-cost and convenient to handle. The syntheses of these heterocycles are the first examples of Co(III)-catalyzed additions to aldehydes, and reactions are demonstrated for a variety of aromatic, heteroaromatic, and aliphatic derivatives. The syntheses of both N-aryl-2H-indazoles and furans have been performed on 20 mmol scales and should be readily applicable to larger scales. The reported heterocycle syntheses also demonstrate the use of directing groups that have not previously been applied to Co(III)-catalyzed C–H bond functionalizations. Additionally, the synthesis of furans demonstrates the first example of Co(III)-catalyzed functionalization of alkenyl C–H bonds. PMID:25494296

  2. Cobalt(III)-catalyzed synthesis of indazoles and furans by C-H bond functionalization/addition/cyclization cascades.

    PubMed

    Hummel, Joshua R; Ellman, Jonathan A

    2015-01-14

    The development of operationally straightforward and cost-effective routes for the assembly of heterocycles from simple inputs is important for many scientific endeavors, including pharmaceutical, agrochemical, and materials research. In this article we describe the development of a new air-stable cationic Co(III) catalyst for convergent, one-step benchtop syntheses of N-aryl-2H-indazoles and furans by C-H bond additions to aldehydes followed by in situ cyclization and aromatization. Only a substoichiometric amount of AcOH is required as an additive that is both low-cost and convenient to handle. The syntheses of these heterocycles are the first examples of Co(III)-catalyzed additions to aldehydes, and reactions are demonstrated for a variety of aromatic, heteroaromatic, and aliphatic derivatives. The syntheses of both N-aryl-2H-indazoles and furans have been performed on 20 mmol scales and should be readily applicable to larger scales. The reported heterocycle syntheses also demonstrate the use of directing groups that have not previously been applied to Co(III)-catalyzed C-H bond functionalizations. Additionally, the synthesis of furans demonstrates the first example of Co(III)-catalyzed functionalization of alkenyl C-H bonds.

  3. Control of oxo-group functionalization and reduction of the uranyl ion.

    PubMed

    Arnold, Polly L; Pécharman, Anne-Frédérique; Lord, Rianne M; Jones, Guy M; Hollis, Emmalina; Nichol, Gary S; Maron, Laurent; Fang, Jian; Davin, Thomas; Love, Jason B

    2015-04-06

    Uranyl complexes of a large, compartmental N8-macrocycle adopt a rigid, "Pacman" geometry that stabilizes the U(V) oxidation state and promotes chemistry at a single uranyl oxo-group. We present here new and straightforward routes to singly reduced and oxo-silylated uranyl Pacman complexes and propose mechanisms that account for the product formation, and the byproduct distributions that are formed using alternative reagents. Uranyl(VI) Pacman complexes in which one oxo-group is functionalized by a single metal cation are activated toward single-electron reduction. As such, the addition of a second equivalent of a Lewis acidic metal complex such as MgN″2 (N″ = N(SiMe3)2) forms a uranyl(V) complex in which both oxo-groups are Mg functionalized as a result of Mg-N bond homolysis. In contrast, reactions with the less Lewis acidic complex [Zn(N″)Cl] favor the formation of weaker U-O-Zn dative interactions, leading to reductive silylation of the uranyl oxo-group in preference to metalation. Spectroscopic, crystallographic, and computational analysis of these reactions and of oxo-metalated products isolated by other routes have allowed us to propose mechanisms that account for pathways to metalation or silylation of the exo-oxo-group.

  4. Microplastic moves pollutants and additives to worms, reducing functions linked to health and biodiversity.

    PubMed

    Browne, Mark Anthony; Niven, Stewart J; Galloway, Tamara S; Rowland, Steve J; Thompson, Richard C

    2013-12-02

    Inadequate products, waste management, and policy are struggling to prevent plastic waste from infiltrating ecosystems [1, 2]. Disintegration into smaller pieces means that the abundance of micrometer-sized plastic (microplastic) in habitats has increased [3] and outnumbers larger debris [2, 4]. When ingested by animals, plastic provides a feasible pathway to transfer attached pollutants and additive chemicals into their tissues [5-15]. Despite positive correlations between concentrations of ingested plastic and pollutants in tissues of animals, few, if any, controlled experiments have examined whether ingested plastic transfers pollutants and additives to animals. We exposed lugworms (Arenicola marina) to sand with 5% microplastic that was presorbed with pollutants (nonylphenol and phenanthrene) and additive chemicals (Triclosan and PBDE-47). Microplastic transferred pollutants and additive chemicals into gut tissues of lugworms, causing some biological effects, although clean sand transferred larger concentrations of pollutants into their tissues. Uptake of nonylphenol from PVC or sand reduced the ability of coelomocytes to remove pathogenic bacteria by >60%. Uptake of Triclosan from PVC diminished the ability of worms to engineer sediments and caused mortality, each by >55%, while PVC alone made worms >30% more susceptible to oxidative stress. As global microplastic contamination accelerates, our findings indicate that large concentrations of microplastic and additives can harm ecophysiological functions performed by organisms.

  5. Differential activation of an identified motor neuron and neuromodulation provide Aplysia's retractor muscle an additional function.

    PubMed

    McManus, Jeffrey M; Lu, Hui; Cullins, Miranda J; Chiel, Hillel J

    2014-08-15

    To survive, animals must use the same peripheral structures to perform a variety of tasks. How does a nervous system employ one muscle to perform multiple functions? We addressed this question through work on the I3 jaw muscle of the marine mollusk Aplysia californica's feeding system. This muscle mediates retraction of Aplysia's food grasper in multiple feeding responses and is innervated by a pool of identified neurons that activate different muscle regions. One I3 motor neuron, B38, is active in the protraction phase, rather than the retraction phase, suggesting the muscle has an additional function. We used intracellular, extracellular, and muscle force recordings in several in vitro preparations as well as recordings of nerve and muscle activity from intact, behaving animals to characterize B38's activation of the muscle and its activity in different behavior types. We show that B38 specifically activates the anterior region of I3 and is specifically recruited during one behavior, swallowing. The function of this protraction-phase jaw muscle contraction is to hold food; thus the I3 muscle has an additional function beyond mediating retraction. We additionally show that B38's typical activity during in vivo swallowing is insufficient to generate force in an unmodulated muscle and that intrinsic and extrinsic modulation shift the force-frequency relationship to allow contraction. Using methods that traverse levels from individual neuron to muscle to intact animal, we show how regional muscle activation, differential motor neuron recruitment, and neuromodulation are key components in Aplysia's generation of multifunctionality.

  6. Effects of spatial grouping on the functional response of predators

    USGS Publications Warehouse

    Cosner, C.; DeAngelis, D.L.; Ault, J.S.; Olson, D.B.

    1999-01-01

    A unified mechanistic approach is given for the derivation of various forms of functional response in predator-prey models. The derivation is based on the principle-of-mass action but with the crucial refinement that the nature of the spatial distribution of predators and/or opportunities for predation are taken into account in an implicit way. If the predators are assumed to have a homogeneous spatial distribution, then the derived functional response is prey-dependent. If the predators are assumed to form a dense colony or school in a single (possibly moving) location, or if the region where predators can encounter prey is assumed to be of limited size, then the functional response depends on both predator and prey densities in a manner that reflects feeding interference between predators. Depending on the specific assumptions, the resulting functional response may be of Beddington-DeAngelis type, of Hassell-Varley type, or ratio-dependent.

  7. Nonequilibrium functional renormalization group for interacting quantum systems.

    PubMed

    Jakobs, Severin G; Meden, Volker; Schoeller, Herbert

    2007-10-12

    We propose a nonequilibrium version of functional renormalization within the Keldysh formalism by introducing a complex-valued flow parameter in the Fermi or Bose functions of each reservoir. Our cutoff scheme provides a unified approach to equilibrium and nonequilibrium situations. We apply it to nonequilibrium transport through an interacting quantum wire coupled to two reservoirs and show that the nonequilibrium occupation induces new power law exponents for the conductance.

  8. Nitric oxide and S-nitrosoglutathione function additively during plant immunity.

    PubMed

    Yun, Byung-Wook; Skelly, Michael J; Yin, Minghui; Yu, Manda; Mun, Bong-Gyu; Lee, Sang-Uk; Hussain, Adil; Spoel, Steven H; Loake, Gary J

    2016-07-01

    Nitric oxide (NO) is emerging as a key regulator of diverse plant cellular processes. A major route for the transfer of NO bioactivity is S-nitrosylation, the addition of an NO moiety to a protein cysteine thiol forming an S-nitrosothiol (SNO). Total cellular levels of protein S-nitrosylation are controlled predominantly by S-nitrosoglutathione reductase 1 (GSNOR1) which turns over the natural NO donor, S-nitrosoglutathione (GSNO). In the absence of GSNOR1 function, GSNO accumulates, leading to dysregulation of total cellular S-nitrosylation. Here we show that endogenous NO accumulation in Arabidopsis, resulting from loss-of-function mutations in NO Overexpression 1 (NOX1), led to disabled Resistance (R) gene-mediated protection, basal resistance and defence against nonadapted pathogens. In nox1 plants both salicylic acid (SA) synthesis and signalling were suppressed, reducing SA-dependent defence gene expression. Significantly, expression of a GSNOR1 transgene complemented the SNO-dependent phenotypes of paraquat resistant 2-1 (par2-1) plants but not the NO-related characters of the nox1-1 line. Furthermore, atgsnor1-3 nox1-1 double mutants supported greater bacterial titres than either of the corresponding single mutants. Our findings imply that GSNO and NO, two pivotal redox signalling molecules, exhibit additive functions and, by extension, may have distinct or overlapping molecular targets during both immunity and development.

  9. Accessing siloxane functionalized polynorbornenes via vinyl-addition polymerization for CO2 separation membranes

    SciTech Connect

    Mahurin, Shannon Mark; Sokolov, Alexei P.; Saito, Tomonori; Long, Brian K.; Gmernicki, Kevin R.; Hong, Eunice; Maroon, Christopher R.

    2016-07-06

    Here, the vinyl addition polymerization of norbornylbased monomers bearing polar functional groups is often problematic, leading to low molecular weight polymers in poor yield. Herein, we provide proof-of-principle evidence that addition-type homopolymers of siloxane substituted norbornyl-based monomers may be readily synthesized using the catalyst trans-[Ni(C6F5)2(SbPh3)2]. Polymerizations using this catalyst reached moderate to high conversion in just 5 min of polymerization and produced siloxanesubstituted polymers with molecular weights exceeding 100 kg/mol. These polymers showed excellent thermal stability (Td ≥ 362 °C) and were cast into membranes that displayed high CO2 permeability and enhanced CO2/N2 selectivity as compared to related materials.

  10. Functional group-specific traits drive phytoplankton dynamics in the oligotrophic ocean.

    PubMed

    Alexander, Harriet; Rouco, Mónica; Haley, Sheean T; Wilson, Samuel T; Karl, David M; Dyhrman, Sonya T

    2015-11-03

    A diverse microbial assemblage in the ocean is responsible for nearly half of global primary production. It has been hypothesized and experimentally demonstrated that nutrient loading can stimulate blooms of large eukaryotic phytoplankton in oligotrophic systems. Although central to balancing biogeochemical models, knowledge of the metabolic traits that govern the dynamics of these bloom-forming phytoplankton is limited. We used eukaryotic metatranscriptomic techniques to identify the metabolic basis of functional group-specific traits that may drive the shift between net heterotrophy and autotrophy in the oligotrophic ocean. Replicated blooms were simulated by deep seawater (DSW) addition to mimic nutrient loading in the North Pacific Subtropical Gyre, and the transcriptional responses of phytoplankton functional groups were assayed. Responses of the diatom, haptophyte, and dinoflagellate functional groups in simulated blooms were unique, with diatoms and haptophytes significantly (95% confidence) shifting their quantitative metabolic fingerprint from the in situ condition, whereas dinoflagellates showed little response. Significantly differentially abundant genes identified the importance of colimitation by nutrients, metals, and vitamins in eukaryotic phytoplankton metabolism and bloom formation in this system. The variable transcript allocation ratio, used to quantify transcript reallocation following DSW amendment, differed for diatoms and haptophytes, reflecting the long-standing paradigm of phytoplankton r- and K-type growth strategies. Although the underlying metabolic potential of the large eukaryotic phytoplankton was consistently present, the lack of a bloom during the study period suggests a crucial dependence on physical and biogeochemical forcing, which are susceptible to alteration with changing climate.

  11. Functional group-specific traits drive phytoplankton dynamics in the oligotrophic ocean

    PubMed Central

    Alexander, Harriet; Rouco, Mónica; Haley, Sheean T.; Wilson, Samuel T.; Karl, David M.; Dyhrman, Sonya T.

    2015-01-01

    A diverse microbial assemblage in the ocean is responsible for nearly half of global primary production. It has been hypothesized and experimentally demonstrated that nutrient loading can stimulate blooms of large eukaryotic phytoplankton in oligotrophic systems. Although central to balancing biogeochemical models, knowledge of the metabolic traits that govern the dynamics of these bloom-forming phytoplankton is limited. We used eukaryotic metatranscriptomic techniques to identify the metabolic basis of functional group-specific traits that may drive the shift between net heterotrophy and autotrophy in the oligotrophic ocean. Replicated blooms were simulated by deep seawater (DSW) addition to mimic nutrient loading in the North Pacific Subtropical Gyre, and the transcriptional responses of phytoplankton functional groups were assayed. Responses of the diatom, haptophyte, and dinoflagellate functional groups in simulated blooms were unique, with diatoms and haptophytes significantly (95% confidence) shifting their quantitative metabolic fingerprint from the in situ condition, whereas dinoflagellates showed little response. Significantly differentially abundant genes identified the importance of colimitation by nutrients, metals, and vitamins in eukaryotic phytoplankton metabolism and bloom formation in this system. The variable transcript allocation ratio, used to quantify transcript reallocation following DSW amendment, differed for diatoms and haptophytes, reflecting the long-standing paradigm of phytoplankton r- and K-type growth strategies. Although the underlying metabolic potential of the large eukaryotic phytoplankton was consistently present, the lack of a bloom during the study period suggests a crucial dependence on physical and biogeochemical forcing, which are susceptible to alteration with changing climate. PMID:26460011

  12. Effects of Oxygen-Containing Functional Groups on Supercapacitor Performance

    SciTech Connect

    Kerisit, Sebastien N.; Schwenzer, Birgit; Vijayakumar, M.

    2014-07-03

    Molecular dynamics (MD) simulations of the interface between graphene and the ionic liquid 1-butyl-3-methylimidazolium trifluoromethanesulfonate (BMIM OTf) were carried out to gain molecular-level insights into the performance of graphene-based supercapacitors and, in particular, determine the effects of the presence of oxygen-containing defects at the graphene surface on their integral capacitance. The MD simulations predict that increasing the surface coverage of hydroxyl groups negatively affects the integral capacitance, whereas the effect of the presence of epoxy groups is much less significant. The calculated variations in capacitance are found to be directly correlated to the interfacial structure. Indeed, hydrogen bonding between hydroxyl groups and SO3 anion moieties prevents BMIM+ and OTf- molecules from interacting favorably in the dense interfacial layer and restrains the orientation and mobility of OTf- ions, thereby reducing the permittivity of the ionic liquid at the interface. The results of the molecular simulations can facilitate the rational design of electrode materials for supercapacitors.

  13. Evaluation of the performance of smoothing functions in generalized additive models for spatial variation in disease.

    PubMed

    Siangphoe, Umaporn; Wheeler, David C

    2015-01-01

    Generalized additive models (GAMs) with bivariate smoothing functions have been applied to estimate spatial variation in risk for many types of cancers. Only a handful of studies have evaluated the performance of smoothing functions applied in GAMs with regard to different geographical areas of elevated risk and different risk levels. This study evaluates the ability of different smoothing functions to detect overall spatial variation of risk and elevated risk in diverse geographical areas at various risk levels using a simulation study. We created five scenarios with different true risk area shapes (circle, triangle, linear) in a square study region. We applied four different smoothing functions in the GAMs, including two types of thin plate regression splines (TPRS) and two versions of locally weighted scatterplot smoothing (loess). We tested the null hypothesis of constant risk and detected areas of elevated risk using analysis of deviance with permutation methods and assessed the performance of the smoothing methods based on the spatial detection rate, sensitivity, accuracy, precision, power, and false-positive rate. The results showed that all methods had a higher sensitivity and a consistently moderate-to-high accuracy rate when the true disease risk was higher. The models generally performed better in detecting elevated risk areas than detecting overall spatial variation. One of the loess methods had the highest precision in detecting overall spatial variation across scenarios and outperformed the other methods in detecting a linear elevated risk area. The TPRS methods outperformed loess in detecting elevated risk in two circular areas.

  14. Evaluation of the Performance of Smoothing Functions in Generalized Additive Models for Spatial Variation in Disease

    PubMed Central

    Siangphoe, Umaporn; Wheeler, David C.

    2015-01-01

    Generalized additive models (GAMs) with bivariate smoothing functions have been applied to estimate spatial variation in risk for many types of cancers. Only a handful of studies have evaluated the performance of smoothing functions applied in GAMs with regard to different geographical areas of elevated risk and different risk levels. This study evaluates the ability of different smoothing functions to detect overall spatial variation of risk and elevated risk in diverse geographical areas at various risk levels using a simulation study. We created five scenarios with different true risk area shapes (circle, triangle, linear) in a square study region. We applied four different smoothing functions in the GAMs, including two types of thin plate regression splines (TPRS) and two versions of locally weighted scatterplot smoothing (loess). We tested the null hypothesis of constant risk and detected areas of elevated risk using analysis of deviance with permutation methods and assessed the performance of the smoothing methods based on the spatial detection rate, sensitivity, accuracy, precision, power, and false-positive rate. The results showed that all methods had a higher sensitivity and a consistently moderate-to-high accuracy rate when the true disease risk was higher. The models generally performed better in detecting elevated risk areas than detecting overall spatial variation. One of the loess methods had the highest precision in detecting overall spatial variation across scenarios and outperformed the other methods in detecting a linear elevated risk area. The TPRS methods outperformed loess in detecting elevated risk in two circular areas. PMID:25983545

  15. Molecular weight distribution and functional group profiles of TEMPO-oxidized lyocell fibers.

    PubMed

    Milanovic, Jovana; Schiehser, Sonja; Milanovic, Predrag; Potthast, Antje; Kostic, Mirjana

    2013-10-15

    The effects of TEMPO-mediated oxidation, performed with NaClO, a catalytic amount of NaBr, and 2,2',6,6'-tetramethylpiperidine-1-oxy radical (TEMPO), were studied on lyocell fibers by means of GPC using multiple detection and group-selective fluorescence labeling according to the CCOA and FDAM methodology. The applied method determines functional group content as a sum parameter, as well as functional group profiles in relation to the molecular weight of the cellulose fibers. Both the CHO and COOH profiles, as well as molecular weight alterations, were analyzed. A significant decrease in the average molecular weight was obtained during the first hour of TEMPO-mediated oxidation, but prolonged oxidation time resulted in no strong additional chain scission. Significant amounts of COOH groups were introduced in the high molecular weight fractions by the oxidation with higher concentrations of NaClO (2.42-9.67 mmol NaClO/g fiber) after modification times of 1h or longer.

  16. The Use of Nominal Group Technique to Determine Additional Support Needs for a Group of Victorian TAFE Managers and Senior Educators

    ERIC Educational Resources Information Center

    Bailey, Anthony

    2013-01-01

    The nominal group technique (NGT) is a structured process to gather information from a group. The technique was first described in 1975 and has since become a widely-used standard to facilitate working groups. The NGT is effective for generating large numbers of creative new ideas and for group priority setting. This paper describes the process of…

  17. Group analysis of self-organizing maps based on functional MRI using restricted Frechet means

    PubMed Central

    Fournel, Arnaud P.; Reynaud, Emanuelle; Brammer, Michael J.; Simmons, Andrew; Ginestet, Cedric E.

    2013-01-01

    Studies of functional MRI data are increasingly concerned with the estimation of differences in spatio-temporal networks across groups of subjects or experimental conditions. Unsupervised clustering and independent component analysis (ICA) have been used to identify such spatio-temporal networks. While these approaches have been useful for estimating these networks at the subject-level, comparisons over groups or experimental conditions require further methodological development. In this paper, we tackle this problem by showing how self-organizing maps (SOMs) can be compared within a Frechean inferential framework. Here, we summarize the mean SOM in each group as a Frechet mean with respect to a metric on the space of SOMs. The advantage of this approach is twofold. Firstly, it allows the visualization of the mean SOM in each experimental condition. Secondly, this Frechean approach permits one to draw inference on group differences, using permutation of the group labels. We consider the use of different distance functions, and introduce one extension of the classical sum of minimum distance (SMD) between two SOMs, which take into account the spatial pattern of the fMRI data. The validity of these methods is illustrated on synthetic data. Through these simulations, we show that the two distance functions of interest behave as expected, in the sense that the ones capturing temporal and spatial aspects of the SOMs are more likely to reach significance under simulated scenarios characterized by temporal, spatial [and spatio-temporal] differences, respectively. In addition, a re-analysis of a classical experiment on visually-triggered emotions demonstrates the usefulness of this methodology. In this study, the multivariate functional patterns typical of the subjects exposed to pleasant and unpleasant stimuli are found to be more similar than the ones of the subjects exposed to emotionally neutral stimuli. In this re-analysis, the group-level SOM output units with the

  18. Quantum groups and functional relations for lower rank

    NASA Astrophysics Data System (ADS)

    Nirov, Kh. S.; Razumov, A. V.

    2017-02-01

    A detailed construction of the universal integrability objects related to the integrable systems associated with the quantum loop algebra Uq(L(sl2)) is given. The full proof of the functional relations in the form independent of the representation of the quantum loop algebra on the quantum space is presented. The case of the general gradation and general twisting is treated. The specialization of the universal functional relations to the case when the quantum space is the state space of a discrete spin chain is described. This is a digression of the corresponding consideration for the case of the quantum loop algebra Uq(L(sl3)) with an extension to the higher spin case.

  19. Multivariate sequence analysis reveals additional function impacting residues in the SDR superfamily.

    PubMed

    Tiwari, Pratibha; Singh, Noopur; Dixit, Aparna; Choudhury, Devapriya

    2014-10-01

    The "extended" type of short chain dehydrogenases/reductases (SDR), share a remarkable similarity in their tertiary structures inspite of being highly divergent in their functions and sequences. We have carried out principal component analysis (PCA) on structurally equivalent residue positions of 10 SDR families using information theoretic measures like Jensen-Shannon divergence and average shannon entropy as variables. The results classify residue positions in the SDR fold into six groups, one of which is characterized by low Shannon entropies but high Jensen-Shannon divergence against the reference family SDR1E, suggesting that these positions are responsible for the specific functional identities of individual SDR families, distinguishing them from the reference family SDR1E. Site directed mutagenesis of three residues from this group in the enzyme UDP-Galactose 4-epimerase belonging to SDR1E shows that the mutants promote the formation of NADH containing abortive complexes. Finally, molecular dynamics simulations have been used to suggest a mechanism by which the mutants interfere with the re-oxidation of NADH leading to the formation of abortive complexes.

  20. Functionalization of metal-organic frameworks through the postsynthetic transformation of olefin side groups.

    PubMed

    Hindelang, Konrad; Kronast, Alexander; Vagin, Sergei I; Rieger, Bernhard

    2013-06-17

    For the first time, the adaptability of the C=C double bond as a versatile precursor for the postsynthetic modification (PSM) of microporous materials was extensively investigated and evaluated. Therefore, an olefin-tagged 4,4'-bipyridine linker was synthesized and successfully introduced as pillar linker within a 9,10-triptycenedicarboxylate (TDC) zinc paddle-wheel metal-organic framework (MOF) through microwave-assisted synthesis. Different reactions, predominately used in organic chemistry, were tested, leading to the development of new postsynthetic reactions for the functionalization of solid materials. The postsynthetic oxidation of the olefin side groups applying osmium tetroxide (OsO₄) as a catalyst led to the formation of a microporous material with free vicinal diol functionalities. The epoxidation with dimethyldioxirane (DMDO) enabled the synthesis of epoxy-functionalized MOFs. In addition to that, reaction procedures for a postsynthetic hydroboration with borane dimethyl sulfide as well as a photoinduced thiol-ene click reaction with ethyl mercaptan were developed. For all of these PSMs, yields of more than 90% were obtained, entirely maintaining the crystallinity of the MOFs. Since the direct introduction of the corresponding groups by means of pre-synthetic approaches is hardly possible, these new PSMs are useful tools for the functionalization of porous solids towards applications such as selective adsorption, separation, and catalysis.

  1. The electrokinetic characterization of gold nanoparticles, functionalized with cationic functional groups, and its' interaction with DNA.

    PubMed

    Lazarus, Geraldine Genevive; Revaprasadu, Neerish; López-Viota, Julián; Singh, Moganavelli

    2014-09-01

    Gold nanoparticles have attracted strong biomedical interest for drug delivery due to their low toxic nature, surface plasmon resonance and capability of increasing the stability of the payload. However, gene transfection represents another important biological application. Considering that cellular barriers keep enclosed their secret to deliver genes using nanoparticles, an important step can be achieved by studying the functionalization of nanoparticles with DNA. In the present contribution the synthesis of nanoparticles consisting of a gold core coated with one or more layers of amino acid (l-lysine), and cationic polyelectrolytes (poly-ethyleneimine and poly-l-lysine) is reported. All nanoparticles were subjected to dynamic light scattering, electrophoretic mobility measurements, UV-vis optical spectrophotometry analysis and transmission electron microscopy imaging. In addition, the adsorption of DNA plasmid (pSGS) with linear and supercoiled configurations was studied for those gold nanoparticles under the most suitable surface modifications. Preliminary results showed that the gold nanoparticles functionalized with poly-ethyleneimine and poly-l-lysine, respectively, and bound to linear DNA configurations, present in absolute value a higher electrophoretic mobility irrespective of the pH of the media, compared to the supercoiled and nicked configuration. The findings from this study suggest that poly-ethyleneimine and poly-l-lysine functionalized gold nanoparticles are biocompatible and may be promising in the chemical design and future optimization of nanostructures for biomedical applications such as gene and drug delivery.

  2. Chemical Assignment of Symmetry-Adapted Perturbation Theory Interaction Energy Components: The Functional-Group SAPT Partition.

    PubMed

    Parrish, Robert M; Parker, Trent M; Sherrill, C David

    2014-10-14

    Recently, we introduced an effective atom-pairwise partition of the many-body symmetry-adapted perturbation theory (SAPT) interaction energy decomposition, producing a method known as atomic SAPT (A-SAPT) [Parrish, R. M.; Sherrill, C. D. J. Chem. Phys. 2014, 141, 044115]. A-SAPT provides ab initio atom-pair potentials for force field development and also automatic visualizations of the spatial contributions of noncovalent interactions, but often has difficulty producing chemically useful partitions of the electrostatic energy, due to the buildup of oscillating partial charges on adjacent functional groups. In this work, we substitute chemical functional groups in place of atoms as the relevant local quasiparticles in the partition, resulting in a functional-group-pairwise partition denoted as functional-group SAPT (F-SAPT). F-SAPT assigns integral sets of local occupied electronic orbitals and protons to chemical functional groups and linking σ bonds. Link-bond contributions can be further assigned to chemical functional groups to simplify the analysis. This approach yields a SAPT partition between pairs of functional groups with integral charge (usually neutral), preventing oscillations in the electrostatic partition. F-SAPT qualitatively matches chemical intuition and the cut-and-cap fragmentation technique but additionally yields the quantitative many-body SAPT interaction energy. The conceptual simplicity, chemical utility, and computational efficiency of F-SAPT is demonstrated in the context of phenol dimer, proflavine(+)-DNA intercalation, and a cucurbituril host-guest inclusion complex.

  3. Two-Year Comparison of a Stream Macroinvertebrate Functional Group Bioassessment Protocol for the Republic of Palau Archipelago

    NASA Astrophysics Data System (ADS)

    Olesen, A. A.; Benbow, M. E.; Holm, T.; Burky, A. J.

    2005-05-01

    Macroinvertebrate functional feeding group data was collected in 2003 and 2004 to develop a rapid bioassessment protocol for Palauan streams. One reference stream, Ngardmau, was selected to test functional group ratios and associated ecosystem attributes against streams of variable impact. In both years qualitative samples were collected using 30s dip net samples in pool habitats and benthic scouring methods in cascades with additional quantitative cascade collections for sampling technique comparisons in 2004. In the reference stream riffle habitat, filtering-gatherers dominated the community (89.92% in 2003 and 47.37% in 2004) compared to all other functional groups. Among the impacted streams, riffle functional group composition was variable compared to the reference stream. In reference pool habitats, gathering-collectors and scrapers dominated in 2003 and 2004, respectively. Scrapers dominated pool habitats of impacted streams in 2004, with some functional groups missing. Changes in ecosystem attributes followed functional group variability depending on degree of impact. Functional group ratios indicated channel stability ratio ([filtering-collectors + scrapers]/[shredders + gathering-collectors]) was lowered with increasing impact, suggesting food and/or habitat quality for filtering-collectors was degraded in riffle habitats in 2003 with no trends in 2004. By this protocol streams were determined to be degraded in 2004 relative to 2003.

  4. Influence of substituents and functional groups on the surface composition of ionic liquids.

    PubMed

    Kolbeck, Claudia; Niedermaier, Inga; Deyko, Alexey; Lovelock, Kevin R J; Taccardi, Nicola; Wei, Wei; Wasserscheid, Peter; Maier, Florian; Steinrück, Hans-Peter

    2014-04-01

    We have performed a systematic study addressing the surface behavior of a variety of functionalized and non-functionalized ionic liquids (ILs). From angle-resolved X-ray photoelectron spectroscopy, detailed conclusions on the surface enrichment of the functional groups and the molecular orientation of the cations and anions is derived. The systems include imidazolium-based ILs methylated at the C2 position, a phenyl-functionalized IL, an alkoxysilane-functionalized IL, halo-functionalized ILs, thioether-functionalized ILs, and amine-functionalized ILs. The results are compared with the results for corresponding non-functionalized ILs where available. Generally, enrichment of the functional group at the surface is only observed for systems that have very weak interaction between the functional group and the ionic head groups.

  5. Extended Functional Groups (EFG): An Efficient Set for Chemical Characterization and Structure-Activity Relationship Studies of Chemical Compounds.

    PubMed

    Salmina, Elena S; Haider, Norbert; Tetko, Igor V

    2015-12-23

    The article describes a classification system termed "extended functional groups" (EFG), which are an extension of a set previously used by the CheckMol software, that covers in addition heterocyclic compound classes and periodic table groups. The functional groups are defined as SMARTS patterns and are available as part of the ToxAlerts tool (http://ochem.eu/alerts) of the On-line CHEmical database and Modeling (OCHEM) environment platform. The article describes the motivation and the main ideas behind this extension and demonstrates that EFG can be efficiently used to develop and interpret structure-activity relationship models.

  6. Integrating products of Bessel functions with an additional exponential or rational factor

    NASA Astrophysics Data System (ADS)

    Van Deun, Joris; Cools, Ronald

    2008-04-01

    We provide two MATLAB programs to compute integrals of the form ex∏i=1kJν_i(ax)dxand 0∞xr+x∏i=1kJν_i(ax)dx with Jν_i(x) the Bessel function of the first kind and (real) order ν. The parameter m is a real number such that ∑ν+m>-1 (to assure integrability near zero), r is real and the numbers c and a are all strictly positive. The program can deliver accurate error estimates. Program summaryProgram title: BESSELINTR, BESSELINTC Catalogue identifier: AEAH_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEAH_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 1601 No. of bytes in distributed program, including test data, etc.: 13 161 Distribution format: tar.gz Programming language: Matlab (version ⩾6.5), Octave (version ⩾2.1.69) Computer: All supporting Matlab or Octave Operating system: All supporting Matlab or Octave RAM: For k Bessel functions our program needs approximately ( 500+140k) double precision variables Classification: 4.11 Nature of problem: The problem consists in integrating an arbitrary product of Bessel functions with an additional rational or exponential factor over a semi-infinite interval. Difficulties arise from the irregular oscillatory behaviour and the possible slow decay of the integrand, which prevents truncation at a finite point. Solution method: The interval of integration is split into a finite and infinite part. The integral over the finite part is computed using Gauss-Legendre quadrature. The integrand on the infinite part is approximated using asymptotic expansions and this approximation is integrated exactly with the aid of the upper incomplete gamma function. In the case where a rational factor is present, this factor is first expanded in a Taylor series around infinity. Restrictions: Some (and eventually all

  7. A mechanistic study of manganese(iii) acetate-mediated phosphonyl group additions to [60]- and [70]-fullerenes: the oxidative-ion-transfer mechanism vs. free radical addition.

    PubMed

    Tumanskii, Boris L; Sabirov, Denis S; Lyakhovetsky, Yury I

    2016-11-14

    The phosphonylation of C60 with HP(O)(OAlk)2 and Mn(OAc)3·2H2O has been considered to occur via a free radical (FR) path involving intermediate radicals ˙P(O)(OAlk)2. The present study provides evidence in support of another mechanism for the reactions, oxidative-ion-transfer (OIT). The mechanism involves the change of an acetate group in Mn(OAc)3 for the phosphonate group and oxidation of C60 by the Mn(OAc)2P(O)(OAlk)2 formed to a pair: (C60˙(+), Mn(OAc)2P(O)(OAlk)2˙(-)) followed by the transfer of the phosphonate anion to give the monophposphonylfullerenyl radical. It undergoes reversible dimerization. The polyaddition occurs analogously. Moreover, the compounds Mn(OAc)2P(O)(OAlk)2 (Alk = Et and i-Pr) obtained make novel reagents for phosphonylation of fullerenes working by the OIT mechanism. The reactions of C60 in benzene with equimolar amounts of Mn(OAc)2P(O)(OPr-i)2 or Hg[P(O)(OPr-i)2]2 which is known as working by the FR mechanism since it produces radical ˙P(O)(OPr-i)2 under UV-irradiation, furnished the same radical ˙C60P(O)(OPr-i)2. However, at a 20-fold molar excess of the reagent toward C60, a single derivative C60[P(O)(OPr-i)2]4 and a mixture of derivatives bearing between two and eight phosphonyls were obtained in the former and latter cases, respectively. With C70, the change of the mechanism produced a change in the regioselectivity: 5 and 3 isomers of ˙C70P(O)(OPr-i)2 were obtained, respectively. DFT-calculations provided the hyperfine coupling (hfc) constants of the isomers and explained the regioselectivity change.

  8. Group additivity equations of state for calculating the standard molal thermodynamic properties of aqueous organic species at elevated temperatures and pressures

    NASA Astrophysics Data System (ADS)

    Amend, Jan P.; Helgeson, Harold C.

    1997-01-01

    Group additivity equations of state for aqueous organic molecules have been generated by combining the revised Helgeson-Kirkham-Flowers (HKF) equations of state ( Shock and Helgeson, 1988, 1990; Tanger and Helgeson, 1988; Shock et al., 1989, 1992) with experimental values of the standard molal properties of aqueous alkanes, alkanols, alkylbenzenes, car☐ylic acids, amides, and amines. Equations of state parameters for the groups represented by -CH 2-, -CH 3, -CHCH 3-, -C 6H 5, -CH 2OH, -COOH, -CONH 2, and -CH 2NH 2 were determined by regression of the experimental data. This procedure permits calculation of the standard molal thermodynamic properties of these groups at elevated temperatures and pressures. Although curves representing the apparent standard molal Gibbs free energies (Δ G°) and enthalpies (Δ H°) of formation, and the standard molal entropies ( S°) of the groups as a function of temperature and pressure are respectively similar for each of them, the temperature dependence of the standard molal heat capacities ( Cp°) and volumes ( V°) of a number of the groups are quite different from one another. For example, the standard molal heat capacities of the hydrocarbon groups minimize with increasing temperature, but those of -CH 2OH and -CH 2NH 2 maximize. Computed values of Δ G°, Δ H°, S°, Cp°, V°, and the equations of state parameters for the various groups were used together with group additivity relations to generate corresponding values of these properties for aqueous n-alkanes, 2-methylalkanes, n-alkylbenzenes, n-alkanols, n-car☐ylic acids, n-amides, and n-amines at temperatures ≤ 250°C and pressures ≤ 1 kbar. The validity and generality of the equations of state are supported by the fact that predicted equilibrium constants for liquid n-alkane solubility reactions in water compare favorably with experimental values reported in the literature for temperatures as high as 200°C. Furthermore, equilibrium constants for aqueous ethane

  9. Ionic Liquids as Multi-Functional Lubricant Additives to Enhance Engine Efficiency (final report NFE-12-03876)

    SciTech Connect

    Qu, Jun; Luo, Huimin; Toops, Todd J.; West, Brian H.; Blau, Peter Julian; Dai, Sheng; Papke, Brian L.; Gao, Hong; Kheireddin, Bassem; Chen, Cheng

    2016-04-01

    This ORNL-Shell CRADA developed and investigated ionic liquids (ILs) as multifunctional additives for next-generation low-viscosity engine oils. Several groups of oil-miscible ILs were successfully designed and synthesized with high thermal stability, non-corrosiveness, excellent wettability, and most importantly effective anti-scuffing/anti-wear and friction reduction characteristics. Synergistic effects between the common anti-wear additive zinc dialkyldithiophosphate (ZDDP) and a particular group of ILs were discovered with > 30% friction reduction and 70% wear reduction compared with using ZDDP or IL alone. The IL+ZDDP tribofilm distinguishes itself from the IL or ZDDP tribofilms with substantially higher contents of metal phosphates but less metal oxides and sulfur compounds. Notably, it was revealed that the actual concentrations of functional elements on the droplet surface of the oil containing IL+ZDDP are one order magnitude higher than their nominal values. Such significantly increased concentrations of anti-wear agents are presumably expected for the oilsolid interface and believed to be responsible for the superior lubricating performance. A prototype SAE 0W-16 engine oil using a synergistic IL+ZDDP pair as the anti-wear additive has been formulated based on the compatibility between the IL and other additives. Sequence VIE full-scale engine dynamometer tests demonstrated fuel economy improvement (FEI) for this prototype oil and revealed the individual contributions from the lower oil viscosity and reduced boundary friction. The impact of IL and IL+ZDDP on exhaust emission catalyst was investigated using an accelerated small engine aging test and results were benchmarked against ZDDP.

  10. Interactions between cocoa flavanols and inorganic nitrate: additive effects on endothelial function at achievable dietary amounts.

    PubMed

    Rodriguez-Mateos, Ana; Hezel, Michael; Aydin, Hilal; Kelm, Malte; Lundberg, Jon O; Weitzberg, Eddie; Spencer, Jeremy P E; Heiss, Christian

    2015-03-01

    Dietary intervention studies have shown that flavanols and inorganic nitrate can improve vascular function, suggesting that these two bioactives may be responsible for beneficial health effects of diets rich in fruits and vegetables. We aimed to study interactions between cocoa flavanols (CF) and nitrate, focusing on absorption, bioavailability, excretion, and efficacy to increase endothelial function. In a double-blind randomized, dose-response crossover study, flow-mediated dilation (FMD) was measured in 15 healthy subjects before and at 1, 2, 3, and 4 h after consumption of CF (1.4-10.9 mg/kg bw) or nitrate (0.1-10 mg/kg bw). To study flavanol-nitrate interactions, an additional intervention trial was performed with nitrate and CF taken in sequence at low and high amounts. FMD was measured before (0 h) and at 1h after ingestion of nitrate (3 or 8.5 mg/kg bw) or water. Then subjects received a CF drink (2.7 or 10.9 mg/kg bw) or a micro- and macronutrient-matched CF-free drink. FMD was measured at 1, 2, and 4 h thereafter. Blood and urine samples were collected and assessed for CF and nitric oxide (NO) metabolites with HPLC and gas-phase reductive chemiluminescence. Finally, intragastric formation of NO after CF and nitrate consumption was investigated. Both CF and nitrate induced similar intake-dependent increases in FMD. Maximal values were achieved at 1 h postingestion and gradually decreased to reach baseline values at 4 h. These effects were additive at low intake levels, whereas CF did not further increase FMD after high nitrate intake. Nitrate did not affect flavanol absorption, bioavailability, or excretion, but CF enhanced nitrate-related gastric NO formation and attenuated the increase in plasma nitrite after nitrate intake. Both flavanols and inorganic nitrate can improve endothelial function in healthy subjects at intake amounts that are achievable with a normal diet. Even low dietary intake of these bioactives may exert relevant effects on endothelial

  11. Separating the effects of shelter from additional cage enhancements for group-housed BALB/cJ mice.

    PubMed

    Swetter, Brentt J; Karpiak, Christie P; Cannon, J Timothy

    2011-05-20

    Enrichment studies with rodents have demonstrated that cage enhancements can improve animal welfare and performance on common behavioral measures, but few studies have compared more than one type of enrichment or controlled for confounds, and some have revealed undesirable effects including increased aggression. We compared effects on male (n=51) and female (n=52) BALB/cJ mice of three common additions to a standard home cage: shelter, shelter+running wheel, and shelter+novel objects. Mice in all conditions lived in standard sized cages with 3-4 mice per cage. Males evidenced significant condition effects. Shelter increased longevity and maintained low levels of aggression. Adding a running wheel increased aggression over shelter alone, changed behavior in the elevated plus (EP) and open field (OF), and maintained the improved longevity seen in all shelter conditions. Novel objects impacted behavioral measures compared to the standard condition. An Igloo shelter without running wheel creates a very different home cage environment than the same shelter with the running wheel attached. Shelter, with positive impact on animal welfare, minimal effects on some common behavioral measures, and some positive effects on test variance, warrants consideration for routine inclusion with group-housed BALB/cJ males.

  12. Polymerization of 1,3-Dienes with Functional Groups. 4.

    NASA Astrophysics Data System (ADS)

    Takenaka, Katsuhiko; Shibata, Natsuyo; Tsuchida, Shinsuke; Takeshita, Hiroki; Miya, Masamitsu; Shiomi, Tomoo

    Anionic polymerization of N,N-diethyl-2-methylene-3-butenamide (DEA), which is a 1,3-butadiene derivative containing a diethylamide function, was carried out in tetrahydrofurane (THF) under various conditions. When DEA was polymerized in THF at -78°C using potassium naphthalenide (K-Naph) or diphenylmethylpotassium (DPMK) as an initiator, a polymer of predictable molecular weight with a narrow molecular weight distribution was obtained. However, the rate of polymerization was extremely slow to reach 80% conversion after 720 h. When the polymerization temperature was raised to 20°C, a low molecular weight oligomer with a broad molecular weight distribution was obtained because of a chain transfer reaction. On the other hand, no such side reaction occurred even at 20°C, when polymerization was carried out in the presence of LiCl. Also, the chain transfer reaction did not occur in lithium naphthalenide (Li-Naph) initiated polymerization. The microstructure of the polymer prepared using a potassium counter cation was a 1 : 1 mixture of 1,4-E and 1,2- structures. In the case of Li-Naph or DPMK/LiCl systems, the microstructure was a complicated mixture of 1,4-E, 1,4-Z, and 1,2-structures.

  13. Critical effect of dependency groups on the function of networks.

    PubMed

    Parshani, Roni; Buldyrev, Sergey V; Havlin, Shlomo

    2011-01-18

    Current network models assume one type of links to define the relations between the network entities. However, many real networks can only be correctly described using two different types of relations. Connectivity links that enable the nodes to function cooperatively as a network and dependency links that bind the failure of one network element to the failure of other network elements. Here we present an analytical framework for studying the robustness of networks that include both connectivity and dependency links. We show that a synergy exists between the failure of connectivity and dependency links that leads to an iterative process of cascading failures that has a devastating effect on the network stability. We present exact analytical results for the dramatic change in the network behavior when introducing dependency links. For a high density of dependency links, the network disintegrates in a form of a first-order phase transition, whereas for a low density of dependency links, the network disintegrates in a second-order transition. Moreover, opposed to networks containing only connectivity links where a broader degree distribution results in a more robust network, when both types of links are present a broad degree distribution leads to higher vulnerability.

  14. Critical effect of dependency groups on the function of networks

    PubMed Central

    Parshani, Roni; Buldyrev, Sergey V.; Havlin, Shlomo

    2011-01-01

    Current network models assume one type of links to define the relations between the network entities. However, many real networks can only be correctly described using two different types of relations. Connectivity links that enable the nodes to function cooperatively as a network and dependency links that bind the failure of one network element to the failure of other network elements. Here we present an analytical framework for studying the robustness of networks that include both connectivity and dependency links. We show that a synergy exists between the failure of connectivity and dependency links that leads to an iterative process of cascading failures that has a devastating effect on the network stability. We present exact analytical results for the dramatic change in the network behavior when introducing dependency links. For a high density of dependency links, the network disintegrates in a form of a first-order phase transition, whereas for a low density of dependency links, the network disintegrates in a second-order transition. Moreover, opposed to networks containing only connectivity links where a broader degree distribution results in a more robust network, when both types of links are present a broad degree distribution leads to higher vulnerability. PMID:21191103

  15. Combinatorial approach to determine functional group effects on lipidoid-mediated siRNA delivery.

    PubMed

    Mahon, Kerry P; Love, Kevin T; Whitehead, Kathryn A; Qin, June; Akinc, Akin; Leshchiner, Elizaveta; Leshchiner, Ignaty; Langer, Robert; Anderson, Daniel G

    2010-08-18

    The application of RNA interference (RNAi), either in the clinic or in the laboratory, requires safe and effective delivery methods. Here, we develop a combinatorial approach to synthesize a library of delivery vectors based on two lipid-like substrates with known siRNA delivery capabilities. Members of this library have a mixture of lipid-like tails and feature appendages containing hydroxyl, carbamate, ether, or amine functional groups as well as variations in alkyl chain length and branching. Using a luciferase reporter system in HeLa cells, we studied the relationship between lipid chemical modification and delivery performance in vitro. The impact of the functional group was shown to vary depending on the overall amine content and tail number of the delivery vector. Additionally, in vivo performance was evaluated using a Factor VII knockdown assay. Two library members, each containing ether groups, were found to knock down the target protein at levels comparable to those of the parent delivery vector. These results demonstrate that small chemical changes to the delivery vector impact knockdown efficiency and cell viability both in vitro and in vivo. The work described here identifies new materials for siRNA delivery and provides new insight into the parameters for optimized chemical makeup of lipid-like siRNA delivery materials.

  16. Phospha-Michael Addition as a New Click Reaction for Protein Functionalization.

    PubMed

    Lee, Yan-Jiun; Kurra, Yadagiri; Liu, Wenshe R

    2016-03-15

    A new type of click reaction between an alkyl phosphine and acrylamide was developed and applied for site-specific protein labeling in vitro and in live cells. Acrylamide is a small electrophilic olefin that readily undergoes phospha-Michael addition with an alkyl phosphine. Our kinetic study indicated a second-order rate constant of 0.07 m(-1)  s(-1) for the reaction between tris(2-carboxyethyl)phosphine and acrylamide at pH 7.4. To demonstrate its application in protein functionalization, we used a dansyl-phosphine conjugate to successfully label proteins that were site-specifically installed with N(ɛ) -acryloyl-l-lysine and employed a biotin-phosphine conjugate to selectively probe human proteins that were metabolically labeled with N-acryloyl-galactosamine.

  17. Genetic evidence for an additional function of phage T4 gene 32 protein: interaction with ligase.

    PubMed

    Mosig, G; Breschkin, A M

    1975-04-01

    Gene 32 of bacteriophage T4 is essential for DNA replication, recombination, and repair. In an attempt to clarify the role of the corresponding gene product, we have looked for mutations that specifically inactivate one but not all of its functions and for compensating suppressor mutations in other genes. Here we describe a gene 32 ts mutant that does not produce progeny, but in contrast to an am mutant investigated by others, is capable of some primary and secondary DNA replication and of forming "joint" recombinational intermediates after infection of Escherichia coli B at the restrictive temperature. However, parental and progeny DNA strands are not ligated to covalently linked "recombinant" molecules, and single strands of vegetative DNA do not exceed unit length. Progeny production as well as capacity for covalent linkage in this gene 32 ts mutant are partially restored by additional rII mutations. Suppression by rII depends on functioning host ligase [EC 6.5.1.2; poly(deoxyribonucleotide):poly(deoxyribonucleotide) ligase (AMP-forming, NMN-forming)]. This gene 32 ts mutation (unlike some others) in turn suppresses the characteristic plaque morphology of rII mutants. We conclude that gene 32 protein, in addition to its role in DNA replication and in the formation of "joint" recombinational intermediates, interacts with T4 ligase [EC 6.5.1.1; poly(deoxyribonucleotide):poly(deoxyribonucleotide) ligase (AMP-forming)] when recombining DNA strands are covalently linked. The protein of the mutant that we describe here is mainly defective in this interaction, thus inactivating T4 ligase in recombination. Suppressing rII mutations facilitate substitution of host ligase. There is suggestive evidence that these interactions occur at the membrane.

  18. Asymmetric Functional Organozinc Additions to Aldehydes Catalyzed by 1,1′-Bi-2-naphthols (BINOLs)†

    PubMed Central

    2015-01-01

    Conspectus Chiral alcohols are ubiquitous in organic structures. One efficient method to generate chiral alcohols is the catalytic asymmetric addition of a carbon nucleophile to a carbonyl compound since this process produces a C–C bond and a chiral center simultaneously. In comparison with the carbon nucleophiles such as an organolithium or a Grignard reagent, an organozinc reagent possesses the advantages of functional group tolerance and more mild reaction conditions. Catalytic asymmetric reactions of aldehydes with arylzincs, vinylzincs, and alkynylzincs to generate functional chiral alcohols are discussed in this Account. Our laboratory has developed a series of 1,1′-bi-2-naphthol (BINOL)-based chiral catalysts for the asymmetric organozinc addition to aldehydes. It is found that the 3,3′-dianisyl-substituted BINOLs are not only highly enantioselective for the alkylzinc addition to aldehydes, but also highly enantioselective for the diphenylzinc addition to aldehydes. A one-step synthesis has been achieved to incorporate Lewis basic amine groups into the 3,3′-positions of the partially hydrogenated H8BINOL. These H8BINOL–amine compounds have become more generally enantioselective and efficient catalysts for the diphenylzinc addition to aldehydes to produce various types of chiral benzylic alcohols. The application of the H8BINOL–amine catalysts is expanded by using in situ generated diarylzinc reagents from the reaction of aryl iodides with ZnEt2, which still gives high enantioselectivity and good catalytic activity. Such a H8BINOL–amine compound is further found to catalyze the highly enantioselective addition of vinylzincs, in situ generated from the treatment of vinyl iodides with ZnEt2, to aldehydes to give the synthetically very useful chiral allylic alcohols. We have discovered that the unfunctionalized BINOL in combination with ZnEt2 and Ti(OiPr)4 can catalyze the terminal alkyne addition to aldehydes to produce chiral propargylic alcohols

  19. Hydrogen atom addition to the surface of graphene nanoflakes: A density functional theory study

    NASA Astrophysics Data System (ADS)

    Tachikawa, Hiroto

    2017-02-01

    Polycyclic aromatic hydrocarbons (PAHs) provide a 2-dimensional (2D) reaction surface in 3-dimensional (3D) interstellar space and have been utilized as a model of graphene surfaces. In the present study, the reaction of PAHs with atomic hydrogen was investigated by means of density functional theory (DFT) to systematically elucidate the binding nature of atomic hydrogen to graphene nanoflakes. PAHs with n = 4-37 were chosen, where n indicates the number of benzene rings. Activation energies of hydrogen addition to the graphene surface were calculated to be 5.2-7.0 kcal/mol at the CAM-B3LYP/6-311G(d,p) level, which is almost constant for all PAHs. The binding energies of hydrogen atom were slightly dependent on the size (n): 14.8-28.5 kcal/mol. The absorption spectra showed that a long tail is generated at the low-energy region after hydrogen addition to the graphene surface. The electronic states of hydrogenated graphenes were discussed on the basis of theoretical results.

  20. Selectivity descriptors for the Michael addition reaction as obtained from density functional based approaches.

    PubMed

    Madjarova, G; Tadjer, A; Cholakova, Tz P; Dobrev, A A; Mineva, T

    2005-01-20

    Density functional (DF) based numerical approaches for computing orbital and atomic reactivity indices were employed in the study of selectivity descriptors for the 1,4 Michael addition reaction. To this aim, atomic and orbital Fukui indices and atomic softnesses for 2-arylmethylene-1,4-butanolides and N,N-disubstituted phenylacetamides were computed. Further on, these local selectivity descriptors have been rationalized in terms of the Pearson's hard-soft-acid-base principle to explain the observed regioselectivity. It is shown that the methods employed for local (atomic and orbital) reactivity index computations are useful and reliable for prediction of the regioselectivity upon conjugate addition of ambident nucleophiles to 2,3-unsaturated carboxylic esters. All the results reveal similar degree of localization/hardness of the 1,4-butanolides C4 and active alpha-carbon belonging to the N,N-dimethyl-phenylacetamide, while the soft alpha-carbon in LiCH2CN reacts with the soft C2 1,4-butanolide center.

  1. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials.

    PubMed

    Qi, Xuejun; Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite's chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface.

  2. Density functional theory study the effects of oxygen-containing functional groups on oxygen molecules and oxygen atoms adsorbed on carbonaceous materials

    PubMed Central

    Song, Wenwu; Shi, Jianwei

    2017-01-01

    Density functional theory was used to study the effects of different types of oxygen-containing functional groups on the adsorption of oxygen molecules and single active oxygen atoms on carbonaceous materials. During gasification or combustion reactions of carbonaceous materials, oxygen-containing functional groups such as hydroxyl(-OH), carbonyl(-CO), quinone(-O), and carboxyl(-COOH) are often present on the edge of graphite and can affect graphite’s chemical properties. When oxygen-containing functional groups appear on a graphite surface, the oxygen molecules are strongly adsorbed onto the surface to form a four-member ring structure. At the same time, the O-O bond is greatly weakened and easily broken. The adsorption energy value indicates that the adsorption of oxygen molecules changes from physisorption to chemisorption for oxygen-containing functional groups on the edge of a graphite surface. In addition, our results indicate that the adsorption energy depends on the type of oxygen-containing functional group. When a single active oxygen atom is adsorbed on the bridge site of graphite, it gives rise to a stable epoxy structure. Epoxy can cause deformation of the graphite lattice due to the transition of graphite from sp2 to sp3 after the addition of an oxygen atom. For quinone group on the edge of graphite, oxygen atoms react with carbon atoms to form the precursor of CO2. Similarly, the single active oxygen atoms of carbonyl groups can interact with edge carbon atoms to form the precursor of CO2. The results show that oxygen-containing functional groups on graphite surfaces enhance the activity of graphite, which promotes adsorption on the graphite surface. PMID:28301544

  3. Fossil group origins. V. The dependence of the luminosity function on the magnitude gap

    NASA Astrophysics Data System (ADS)

    Zarattini, S.; Aguerri, J. A. L.; Sánchez-Janssen, R.; Barrena, R.; Boschin, W.; del Burgo, C.; Castro-Rodriguez, N.; Corsini, E. M.; D'Onghia, E.; Girardi, M.; Iglesias-Páramo, J.; Kundert, A.; Méndez-Abreu, J.; Vilchez, J. M.

    2015-09-01

    Context. In nature we observe galaxy aggregations that span a wide range of magnitude gaps between the two first-ranked galaxies of a system (Δm12). Thus, there are systems with gaps close to zero (e.g., the Coma cluster), and at the other extreme of the distribution, the largest gaps are found among the so-called fossil systems. The observed distribution of magnitude gaps is thought to be a consequence of the orbital decay of M∗ galaxies in massive halos and the associated growth of the central object. As a result, to first order the amplitude of this gap is a good statistical proxy for the dynamical age of a system of galaxies. Fossil and non-fossil systems could therefore have different galaxy populations that should be reflected in their luminosity functions. Aims: In this work we study, for the first time, the dependence of the luminosity function parameters on Δm12 using data obtained by the fossil group origins (FOGO) project. Methods: We constructed a hybrid luminosity function for 102 groups and clusters at z ≤ 0.25 using both photometric data from the SDSS-DR7 and redshifts from the DR7 and the FOGO surveys. The latter consists of ~1200 new redshifts in 34 fossil system candidates. We stacked all the individual luminosity functions, dividing them into bins of Δm12, and studied their best-fit Schechter parameters. We additionally computed a "relative" luminosity function, expressed as a function of the central galaxy luminosity, which boosts our capacity to detect differences - especially at the bright end. Results: We find trends as a function of Δm12 at both the bright and faint ends of the luminosity function. In particular, at the bright end, the larger the magnitude gap, the fainter the characteristic magnitude M∗. The characteristic luminosity in systems with negligible gaps is more than a factor three brighter than in fossil-like ones. Remarkably, we also find differences at the faint end. In this region, the larger the gap, the flatter

  4. Role of Lewis acid additives in a palladium catalyzed directed C-H functionalization reaction of benzohydroxamic acid to isoxazolone.

    PubMed

    Athira, C; Sunoj, Raghavan B

    2016-12-20

    Metallic salts as well as protic additives are widely employed in transition metal catalyzed C-H bond functionalization reactions to improve the efficiency of catalytic protocols. In one such example, ZnCl2 and pivalic acid are used as additives in a palladium catalyzed synthesis of isoxazolone from a readily available benzohydroxamic acid under one pot conditions. In this article, we present some important mechanistic insights into the role of ZnCl2 and pivalic acid, gained by using density functional theory (M06) computations. Two interesting modes of action of ZnCl2 are identified in various catalytic steps involved in the formation of isoxazolone. The conventional Lewis acid coordination wherein zinc chloride (ZnCl2·(DMA)) binds to the carbonyl group is found to be more favored in the C-H activation step. However, the participation of a hetero-bimetallic Pd-Zn species is preferred in reductive elimination leading to Caryl-N bond formation. Pivalic acid helps in relay proton transfer in C-H bond activation through a cyclometallation deprotonation (CMD) process. The explicit inclusion of ZnCl2 and solvent N,N-dimethyl acetamide (DMA) stabilizes the transition state and also helps reduce the activation barrier for the C-H bond activation step. The electronic communication between the two metal species is playing a crucial role in stabilizing the Caryl-N bond formation transition state through a Pd-Zn hetero-bimetallic interaction.

  5. Next-generation biomedical implants using additive manufacturing of complex, cellular and functional mesh arrays.

    PubMed

    Murr, L E; Gaytan, S M; Medina, F; Lopez, H; Martinez, E; Machado, B I; Hernandez, D H; Martinez, L; Lopez, M I; Wicker, R B; Bracke, J

    2010-04-28

    In this paper, we examine prospects for the manufacture of patient-specific biomedical implants replacing hard tissues (bone), particularly knee and hip stems and large bone (femoral) intramedullary rods, using additive manufacturing (AM) by electron beam melting (EBM). Of particular interest is the fabrication of complex functional (biocompatible) mesh arrays. Mesh elements or unit cells can be divided into different regions in order to use different cell designs in different areas of the component to produce various or continually varying (functionally graded) mesh densities. Numerous design elements have been used to fabricate prototypes by AM using EBM of Ti-6Al-4V powders, where the densities have been compared with the elastic (Young) moduli determined by resonant frequency and damping analysis. Density optimization at the bone-implant interface can allow for bone ingrowth and cementless implant components. Computerized tomography (CT) scans of metal (aluminium alloy) foam have also allowed for the building of Ti-6Al-4V foams by embedding the digital-layered scans in computer-aided design or software models for EBM. Variations in mesh complexity and especially strut (or truss) dimensions alter the cooling and solidification rate, which alters the alpha-phase (hexagonal close-packed) microstructure by creating mixtures of alpha/alpha' (martensite) observed by optical and electron metallography. Microindentation hardness measurements are characteristic of these microstructures and microstructure mixtures (alpha/alpha') and sizes.

  6. Diverse Functions of Restriction-Modification Systems in Addition to Cellular Defense

    PubMed Central

    Vasu, Kommireddy

    2013-01-01

    SUMMARY Restriction-modification (R-M) systems are ubiquitous and are often considered primitive immune systems in bacteria. Their diversity and prevalence across the prokaryotic kingdom are an indication of their success as a defense mechanism against invading genomes. However, their cellular defense function does not adequately explain the basis for their immaculate specificity in sequence recognition and nonuniform distribution, ranging from none to too many, in diverse species. The present review deals with new developments which provide insights into the roles of these enzymes in other aspects of cellular function. In this review, emphasis is placed on novel hypotheses and various findings that have not yet been dealt with in a critical review. Emerging studies indicate their role in various cellular processes other than host defense, virulence, and even controlling the rate of evolution of the organism. We also discuss how R-M systems could have successfully evolved and be involved in additional cellular portfolios, thereby increasing the relative fitness of their hosts in the population. PMID:23471617

  7. Regulatory network reconstruction using an integral additive model with flexible kernel functions

    PubMed Central

    Novikov, Eugene; Barillot, Emmanuel

    2008-01-01

    Background Reconstruction of regulatory networks is one of the most challenging tasks of systems biology. A limited amount of experimental data and little prior knowledge make the problem difficult to solve. Although models that are currently used for inferring regulatory networks are sometimes able to make useful predictions about the structures and mechanisms of molecular interactions, there is still a strong demand to develop increasingly universal and accurate approaches for network reconstruction. Results The additive regulation model is represented by a set of differential equations and is frequently used for network inference from time series data. Here we generalize this model by converting differential equations into integral equations with adjustable kernel functions. These kernel functions can be selected based on prior knowledge or defined through iterative improvement in data analysis. This makes the integral model very flexible and thus capable of covering a broad range of biological systems more adequately and specifically than previous models. Conclusion We reconstructed network structures from artificial and real experimental data using differential and integral inference models. The artificial data were simulated using mathematical models implemented in JDesigner. The real data were publicly available yeast cell cycle microarray time series. The integral model outperformed the differential one for all cases. In the integral model, we tested the zero-degree polynomial and single exponential kernels. Further improvements could be expected if the kernel were selected more specifically depending on the system. PMID:18218091

  8. Cryptic biodiversity effects: importance of functional redundancy revealed through addition of food web complexity.

    PubMed

    Philpott, Stacy M; Pardee, Gabriella L; Gonthier, David J

    2012-05-01

    Interactions between predators and the degree of functional redundancy among multiple predator species may determine whether herbivores experience increased or decreased predation risk. Specialist parasites can modify predator behavior, yet rarely have cascading effects on multiple predator species and prey been evaluated. We examined influences of specialist phorid parasites (Pseudacteon spp.) on three predatory ant species and herbivores in a coffee agroecosystem. Specifically, we examined whether changes in ant richness affected fruit damage by the coffee berry borer (Hypothenemus hampei) and whether phorids altered multi-predator effects. Each ant species reduced borer damage, and without phorids, increasing predator richness did not further decrease borer damage. However, with phorids, activity of one ant species was reduced, indicating that the presence of multiple ant species was necessary to limit borer damage. In addition, phorid presence revealed synergistic effects of multiple ant species, not observed without the presence of this parasite. Thus, a trait-mediated cascade resulting from a parasite-induced predator behavioral change revealed the importance of functional redundancy, predator diversity, and food web complexity for control of this important pest.

  9. A table of integrals of the error function. II - Additions and corrections.

    NASA Technical Reports Server (NTRS)

    Geller, M.; Ng, E. W.

    1971-01-01

    Integrals of products of error functions with other functions are presented, taking into account a combination of the error function with powers, a combination of the error function with exponentials and powers, a combination of the error function with exponentials of more complicated arguments, definite integrals from Laplace transforms, and a combination of the error function with trigonometric functions. Other integrals considered include a combination of the error function with logarithms and powers, a combination of two error functions, and a combination of the error function with other special functions.

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

    PubMed

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

    2012-12-01

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

  11. Soft and Bio Nanomaterials Group at Brookhaven’s Center for Functional Nanomaterials

    SciTech Connect

    Gang, Oleg

    2016-12-07

    Group leader Oleg Gang talks about the methods his group develops to direct the self-assembly of nanoscale systems from organic and inorganic components into functional materials with desired properties.

  12. Soft and Bio Nanomaterials Group at Brookhaven’s Center for Functional Nanomaterials

    ScienceCinema

    Gang, Oleg

    2016-12-14

    Group leader Oleg Gang talks about the methods his group develops to direct the self-assembly of nanoscale systems from organic and inorganic components into functional materials with desired properties.

  13. Thermochemical Properties Enthalpy, Entropy, and Heat Capacity of C1-C4 Fluorinated Hydrocarbons: Fluorocarbon Group Additivity.

    PubMed

    Wang, Heng; Castillo, Álvaro; Bozzelli, Joseph W

    2015-07-23

    Enthalpies of formation for 14 C2–C4 fluorinated hydrocarbons were calculated with nine popular ab initio and density functional theory methods: B3LYP, CBS-QB3, CBS-APNO, M06, M06-2X, ωB97X, G4, G4(MP2)-6X, and W1U via several series of isodesmic reactions. The recommended ideal gas phase ΔHf298° (kcal mol(–1)) values calculated in this study are the following: −65.4 for CH3CH2F; −70.2 for CH3CH2CH2F; −75.3 for CH3CHFCH3; −75.2 for CH3CH2CH2CH2F; −80.3 for CH3CHFCH2CH3; −108.1 for CH2F2; −120.9 for CH3CHF2; −125.8 for CH3CH2CHF2; −133.3 for CH3CF2CH3; −166.7 for CHF3; −180.5 for CH3CF3; −185.5 for CH3CH2CF3; −223.2 for CF4; and −85.8 for (CH3)3CF. Entropies (S298° in cal mol(–1) K(–1)) were estimated using B3LYP/6-31+G(d,p) computed frequencies and geometries. Rotational barriers were determined and hindered internal rotational contributions for S298°, and Cp(T) were calculated using the rigid rotor harmonic oscillator approximation, with direct integration over energy levels of the intramolecular rotation potential energy curve. Thermochemical properties for the fluorinated carbon groups C/C/F/H2, C/C2/F/H, C/C/F2/H, C/C2/F2, and C/C/F3 were derived from the above target fluorocarbons. Previously published enthalpies and groups for 1,2-difluoroethane, 1,1,2-trifluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,1,2,2-pentafluoroethane, 2-fluoro-2-methylpropane that were previously determined via work reaction schemes are revised using updated reference species values. Standard deviations are compared for the calculation methods.

  14. Tunable Oxygen Functional Groups as Electrocatalysts on Graphite Felt Surfaces for All-Vanadium Flow Batteries

    SciTech Connect

    Estevez, Luis; Reed, David; Nie, Zimin; Schwarz, Ashleigh M.; Nandasiri, Manjula I.; Kizewski, James P.; Wang, Wei; Thomsen, Edwin; Liu, Jun; Zhang, Ji-Guang; Sprenkle, Vincent; Li, Bin

    2016-05-17

    We decorated the surfaces of graphite felts with some oxygen-containing functional groups, such as C-OH, O=C and HO-C=O. And the mole ratios and amounts of these functional groups were effectively adjusted on the graphite surface by a particular method. The catalytic effects of amounts and mole ratio of different kinds of functional groups on VRB electrode performances were investigated in detail.

  15. The Additive Impact of Group and Individual Publicly Displayed Feedback: Examining Individual Response Patterns and Response Generalization in a Safe-Driving Occupational Intervention

    ERIC Educational Resources Information Center

    Ludwig, Timothy D.; Geller, E. Scott; Clarke, Steven W.

    2010-01-01

    Additive effects of publicly posting individual feedback following group goal-setting and feedback were evaluated. The turn-signal use of pizza deliverers was studied in a multiple baseline design across two pizza stores. After baseline observations, pizza deliverers voted on a group turn-signal goal and then received 4 weeks of group feedback on…

  16. Adding functionality with additive manufacturing: Fabrication of titanium-based antibiotic eluting implants.

    PubMed

    Cox, Sophie C; Jamshidi, Parastoo; Eisenstein, Neil M; Webber, Mark A; Hassanin, Hany; Attallah, Moataz M; Shepherd, Duncan E T; Addison, Owen; Grover, Liam M

    2016-07-01

    Additive manufacturing technologies have been utilised in healthcare to create patient-specific implants. This study demonstrates the potential to add new implant functionality by further exploiting the design flexibility of these technologies. Selective laser melting was used to manufacture titanium-based (Ti-6Al-4V) implants containing a reservoir. Pore channels, connecting the implant surface to the reservoir, were incorporated to facilitate antibiotic delivery. An injectable brushite, calcium phosphate cement, was formulated as a carrier vehicle for gentamicin. Incorporation of the antibiotic significantly (p=0.01) improved the compressive strength (5.8±0.7MPa) of the cement compared to non-antibiotic samples. The controlled release of gentamicin sulphate from the calcium phosphate cement injected into the implant reservoir was demonstrated in short term elution studies using ultraviolet-visible spectroscopy. Orientation of the implant pore channels were shown, using micro-computed tomography, to impact design reproducibility and the back-pressure generated during cement injection which ultimately altered porosity. The amount of antibiotic released from all implant designs over a 6hour period (<28% of the total amount) were found to exceed the minimum inhibitory concentrations of Staphylococcus aureus (16μg/mL) and Staphylococcus epidermidis (1μg/mL); two bacterial species commonly associated with periprosthetic infections. Antibacterial efficacy was confirmed against both bacterial cultures using an agar diffusion assay. Interestingly, pore channel orientation was shown to influence the directionality of inhibition zones. Promisingly, this work demonstrates the potential to additively manufacture a titanium-based antibiotic eluting implant, which is an attractive alternative to current treatment strategies of periprosthetic infections.

  17. Ecological Significance of a Geomorphic Stream Classification: Species and Functional Group Composition of Riparian Plant Communities

    NASA Astrophysics Data System (ADS)

    Shaw, J. R.; Cooper, D. J.

    2014-12-01

    We tested the ecological significance of a geomorphic classification of Sonoran Desert ephemeral stream channels based on channel plan-form, degree of lateral confinement, and boundary material composition. This typology has been shown to discriminate among channel geometry and hydraulic characteristics for bedrock, bedrock with alluvium, incised alluvium, braided, and piedmont headwater channels. We examined stream reach-scale relationships of geomorphic stream types to the relative cover and density of perennial plant species and functional groups, and identified the dominant fluvial drivers, within riparian communities at 101 ephemeral stream reaches on the U.S. Army Yuma Proving Ground and Barry M. Goldwater Air Force Range in southwestern Arizona, USA. Nonparametric multivariate analysis of variance showed that species and functional group composition differed significantly among geomorphic stream types, both in terms of relative cover and density. Partitioning of among-site multivariate dissimilarity revealed that species compositional differences between stream types were caused largely by variation in the cover and density of the most common members of the regional flora. Distinctive functional group composition among reach types resulted from differences in the cover and density of drought-deciduous shrubs and subshrubs, evergreen trees and shrubs, and photosynthetic-stemmed trees. Comparison of environmental and biotic dissimilarity matrices highlighted the role of channel gradient as the dominant abiotic driver of riparian plant community composition, with stream channel elevation and width:depth providing additional explanatory power. Distinctive riparian plant community composition among the geomorphic stream types demonstrates the ecological significance of this a priori channel classification, and indicates its potential utility in understanding spatial patterns of ecological dynamics, sample stratification for process-based studies, and reference

  18. Thermochemical properties, rotation barriers, and group additivity for unsaturated oxygenated hydrocarbons and radicals resulting from reaction of vinyl and phenyl radical systems with O2.

    PubMed

    Sebbarand, Nadia; Bockhorn, Henning; Bozzelli, Joseph W

    2005-03-17

    Oxidation of unsaturated and aromatic hydrocarbons in atmospheric and combustion processes results in formation of linear and cyclic unsaturated, oxygenated-hydrocarbon intermediates. The thermochemical parameters delatafH degrees 298, S degrees 298, and C(p)(f298)(T) for these intermediates are needed to understand their stability and reaction paths in further oxidation. These properties are not available for a majority of these unsaturated oxy-hydrocarbons and their corresponding radicals, even via group additivity methods. Enthalpy, entropy, and heat capacity of a series of 40 oxygenated and non-oxygenated molecules, or radicals corresponding to hydrogen atom loss from the parent stable molecules are determined in this study. Enthalpy (delatafH degrees 298 in kcal mol(-1)) is derived from the density function calculations at the B3LYP/6-311g(d,p) calculated enthalpy of reaction (delatafH degrees rxn,298) and by use of isodesmic (work) reactions. Estimation of error in enthalpy delatafH degrees 298, from use of computational chemistry coupled with work reactions analysis, is presented using comparisons between the calculated and literature enthalpies of reaction. Entropies (S degrees 298) and heat capacities (C(p)(f298)(T)) were calculated using the B3LYP/6-311G(d,p) determined frequencies and geometries. Potential barriers for internal rotors in each molecule were determined and used (in place of torsion frequencies) to calculate contributions to S and C(p)(T) from the hindered rotors. Twenty-six groups for use in group additivity (GA) are also developed.

  19. A CRM domain protein functions dually in group I and group II intron splicing in land plant chloroplasts.

    PubMed

    Asakura, Yukari; Barkan, Alice

    2007-12-01

    The CRM domain is a recently recognized RNA binding domain found in three group II intron splicing factors in chloroplasts, in a bacterial protein that associates with ribosome precursors, and in a family of uncharacterized proteins in plants. To elucidate the functional repertoire of proteins with CRM domains, we studied CFM2 (for CRM Family Member 2), which harbors four CRM domains. RNA coimmunoprecipitation assays showed that CFM2 in maize (Zea mays) chloroplasts is associated with the group I intron in pre-trnL-UAA and group II introns in the ndhA and ycf3 pre-mRNAs. T-DNA insertions in the Arabidopsis thaliana ortholog condition a defective-seed phenotype (strong allele) or chlorophyll-deficient seedlings with impaired splicing of the trnL group I intron and the ndhA, ycf3-int1, and clpP-int2 group II introns (weak alleles). CFM2 and two previously described CRM proteins are bound simultaneously to the ndhA and ycf3-int1 introns and act in a nonredundant fashion to promote their splicing. With these findings, CRM domain proteins are implicated in the activities of three classes of catalytic RNA: group I introns, group II introns, and 23S rRNA.

  20. Functional Groups Based on Leaf Physiology: Are they Spatially and Temporally Robust?

    NASA Technical Reports Server (NTRS)

    Foster, Tammy E.; Brooks, J. Renee; Quincy, Charles (Technical Monitor)

    2002-01-01

    The functional grouping hypothesis, which suggests that complexity in function can be simplified by grouping species with similar responses, was tested in the Florida scrub habitat. Functional groups were identified based on how species in fire maintained FL scrub function in terms of carbon, water and nitrogen dynamics. The suite of physiologic parameters measured to determine function included both instantaneous gas exchange measurements obtained from photosynthetic light response curves and integrated measures of function. Using cluster analysis, five distinct physiologically-based functional groups were identified. Using non-parametric multivariate analyses, it was determined that these five groupings were not altered by plot differences or by the three different management regimes; prescribed burn, mechanically treated and burn, and fire-suppressed. The physiological groupings also remained robust between the two years 1999 and 2000. In order for these groupings to be of use for scaling ecosystem processes, there needs to be an easy-to-measure morphological indicator of function. Life form classifications were able to depict the physiological groupings more adequately than either specific leaf area or leaf thickness. THe ability of life forms to depict the groupings was improved by separating the parasitic Ximenia americana from the shrub category.

  1. Building functional groups of marine benthic macroinvertebrates on the basis of general community assembly mechanisms

    NASA Astrophysics Data System (ADS)

    Alexandridis, Nikolaos; Bacher, Cédric; Desroy, Nicolas; Jean, Fred

    2017-03-01

    The accurate reproduction of the spatial and temporal dynamics of marine benthic biodiversity requires the development of mechanistic models, based on the processes that shape macroinvertebrate communities. The modelled entities should, accordingly, be able to adequately represent the many functional roles that are performed by benthic organisms. With this goal in mind, we applied the emergent group hypothesis (EGH), which assumes functional equivalence within and functional divergence between groups of species. The first step of the grouping involved the selection of 14 biological traits that describe the role of benthic macroinvertebrates in 7 important community assembly mechanisms. A matrix of trait values for the 240 species that occurred in the Rance estuary (Brittany, France) in 1995 formed the basis for a hierarchical classification that generated 20 functional groups, each with its own trait values. The functional groups were first evaluated based on their ability to represent observed patterns of biodiversity. The two main assumptions of the EGH were then tested, by assessing the preservation of niche attributes among the groups and the neutrality of functional differences within them. The generally positive results give us confidence in the ability of the grouping to recreate functional diversity in the Rance estuary. A first look at the emergent groups provides insights into the potential role of community assembly mechanisms in shaping biodiversity patterns. Our next steps include the derivation of general rules of interaction and their incorporation, along with the functional groups, into mechanistic models of benthic biodiversity.

  2. A comparative study of six different inpatient groups with respect to their basic assumption functioning.

    PubMed

    Karterud, S

    1989-07-01

    Seventy-five group therapy sessions of six different inpatient team groups in one short-term, one intermediate term, and one long-term psychiatric ward were studied with Group Focal Conflict Analysis and the Group Emotionality Rating System. The majority of the group sessions (41) functioned as fight-flight groups, twenty-four sessions functioned at a "pseudogroup" level, and ten sessions were dependency groups. The differences between the fight-flight groups and the dependency group on the variables aggression and dependency were highly significant statistically. A mixture of fight-flight groups and pseudogroups were found in the short-term ward with emergency obligations. The author discusses the assets and shortcomings of fight-flight and dependency cultures within psychiatric wards.

  3. Temperature, pressure, and electrochemical constraints on protein speciation: Group additivity calculation of the standard molal thermodynamic properties of ionized unfolded proteins

    NASA Astrophysics Data System (ADS)

    Dick, J. M.; Larowe, D. E.; Helgeson, H. C.

    2006-07-01

    Thermodynamic calculations can be used to quantify environmental constraints on the speciation of proteins, such as the pH and temperature dependence of ionization state, and the relative chemical stabilities of proteins in different biogeochemical settings. These calculations depend in part on values of the standard molal Gibbs energies of proteins and their ionization reactions as a function of temperature and pressure. Because these values are not generally available, we calculated values of the standard molal thermodynamic properties at 25°C and 1 bar as well as the revised Helgeson-Kirkham-Flowers equations of state parameters of neutral and charged zwitterionic reference model compounds including aqueous amino acids, polypeptides, and unfolded proteins. The experimental calorimetric and volumetric data for these species taken from the literature were combined with group additivity algorithms to calculate the properties and parameters of neutral and ionized sidechain and backbone groups in unfolded proteins. The resulting set of group contributions enables the calculation of the standard molal Gibbs energy, enthalpy, entropy, isobaric heat capacity, volume, and isothermal compressibility of unfolded proteins in a range of proton ionization states to temperatures and pressures exceeding 100°C and 1000 bar. This approach provides a useful frame of reference for thermodynamic studies of protein folding and complexation reactions. It can also be used to assign provisional values of the net charge and Gibbs energy of ionized proteins as a function of temperature and pH. Using these values, an Eh-pH diagram for a reaction representing the speciation of extracellular proteins from Pyrococcus furiosus and Bacillus subtilis was generated. The predicted predominance limits of these proteins correspond with the different electrochemical conditions of hydrothermal vents and soils. More comprehensive calculations of this kind may reveal pervasive chemical potential

  4. [Response of Phytoplankton Functional Groups to Eutrophication in Summer at Xiaoguan Reservoir].

    PubMed

    Li, Lei; Li, Qiu-hua; Jiao, Shu-lin; Li, Yue; Xiao, Jing; Deng, Long; Sun, Rong-guo; Gao, Yong-chun; Luo, Lan

    2015-12-01

    Hydrology and Water Resources Bureau of Guizhou Province, Guiyang 550002, China) Abstract: In order to explore the distribution characteristics of phytoplankton functional groups, eutrophication characteristics and response of phytoplankton functional groups to eutrophication in Xiaoguan Reservoir, phytoplankton and water samples were taken once a week from 25th July 2014 to 27th September 2014. The results showed that there were 22 phytoplankton functional groups, groups S1, D, J, B, G, MP, L₀, SN, X1, Y, Xph, F, T and W1 were comparatively common functional groups, Wherein, S1, D and J were the dominant functional groups. Weekly dynamics of phytoplankton functional groups were: S1-->S1-->S1-->S1-->S1--S1-->S1-->J/D/S1-->Sl1- >/1D. group Sl1dominated over other groups, the cell abundance of S1 appeared two peaks at week 5 and week 7 respectively, but there was a slump at week 8, and rose again at last, compared to two peaks before, the cell abundance had dropped from 10⁸cells · L⁻¹ to 10⁷cells · L⁻¹ Water flush caused by discharge gate opening artificially was the main reason. Based on the three methods of eutrophication evaluation, the water was in moderately eutrophic and eutrophic states in Xiaoguan Reservoir in the summer of 2014. Multivariate analysis (RDA) indicated transparency was the main factor affecting the distribution of phytoplankton functional groups, and nutrients were no longer the limiting factor. The study suggested that phytoplankton functional groups could make a good response to eutrophication: groups S1 and J adapted to the turbid eutrophic water bodies, D adapted to shallow turbid waters and was sensitive to nutrient depletion. Also, common functional groups like G, X1, WW1 F etc. mostly adapted to eutrophic water bodies.

  5. Preparation and ageing-resistant properties of polyester composites modified with functional nanoscale additives

    PubMed Central

    2014-01-01

    This study investigated ageing-resistant properties of carboxyl-terminated polyester (polyethylene glycol terephthalate) composites modified with nanoscale titanium dioxide particles (nano-TiO2). The nano-TiO2 was pretreated by a dry coating method, with aluminate coupling agent as a functional grafting additive. The agglomeration resistance was evaluated, which exhibited significant improvement for the modified nanoparticles. Then, the effects of the modified nano-TiO2 on the crosslinking and ageing-resistant properties of the composites were studied. With a real-time Fourier transform infrared (FT-IR) measurement, the nano-TiO2 displayed promoting effect on the crosslinking of polyester resin with triglycidyl isocyanurate (TGIC) as crosslinking agent. Moreover, the gloss retention, colour aberration and the surface morphologies of the composites during accelerated UV ageing (1500 hours) were investigated. The results demonstrated much less degree of ageing degradation for the nanocomposites, indicating an important role of the nano-TiO2 in improving the ageing-resistant properties of synthetic polymer composites. PMID:24872802

  6. Highly Functionalized Cyclopentane Derivatives by Tandem Michael Addition/Radical Cyclization/Oxygenation Reactions.

    PubMed

    Holan, Martin; Pohl, Radek; Císařová, Ivana; Klepetářová, Blanka; Jones, Peter G; Jahn, Ullrich

    2015-06-26

    Densely functionalized cyclopentane derivatives with up to four consecutive stereocenters are assembled by a tandem Michael addition/single-electron transfer oxidation/radical cyclization/oxygenation strategy mediated by ferrocenium hexafluorophosphate, a recyclable, less toxic single-electron transfer oxidant. Ester enolates were coupled with α-benzylidene and α-alkylidene β-dicarbonyl compounds with switchable diastereoselectivity. This pivotal steering element subsequently controls the diastereoselectivity of the radical cyclization step. The substitution pattern of the radical cyclization acceptor enables a switch of the cyclization mode from a 5-exo pattern for terminally substituted olefin units to a 6-endo mode for internally substituted acceptors. The oxidative anionic/radical strategy also allows efficient termination by oxygenation with the free radical 2,2,6,6-tetramethyl-1-piperidinoxyl, and two C-C bonds and one C-O bond are thus formed in the sequence. A stereochemical model is proposed that accounts for all of the experimental results and allows the prediction of the stereochemical outcome. Further transformations of the synthesized cyclopentanes are reported.

  7. Density functional theory study of the effects of alloying additions on sulfur adsorption on nickel surfaces

    NASA Astrophysics Data System (ADS)

    Malyi, Oleksandr I.; Chen, Zhong; Kulish, Vadym V.; Bai, Kewu; Wu, Ping

    2013-01-01

    Reactions of hydrogen sulfide (H2S) with Nickel/Ytrria-doped zirconia (Ni/YDZ) anode materials might cause degradation of the performance of solid oxide fuel cells when S containing fuels are used. In this paper, we employ density functional theory to investigate S adsorption on metal (M)-doped and undoped Ni(0 0 1) and Ni(1 1 1) surfaces. Based on the performed calculations, we analyze the effects of 12 alloying additions (Ag, Au, Al, Bi, Cd, Co, Cu, Fe, Sn, Sb, V, and Zn) on the temperature of transition between clean (S atoms do not adsorb on the surfaces) and contaminated (S atoms can adsorb on the surfaces spontaneously) M-doped Ni surfaces for different concentrations of H2S in the fuel. Predicted results are consistent with many experimental studies relevant to S poisoning of both Ni/YDZ and M-doped Ni/YDZ anode materials. This study is important to understand S poisoning phenomena and to develop new S tolerant anode materials.

  8. Controlling light absorption and photoelectric properties of coumarin-triphenylaminedye by different acceptor functional groups.

    PubMed

    Sun, Chaofan; Bai, Yanpeng; Li, Yuanzuo; Liu, Dejiang; Xu, Beibei; Wang, Qungui

    2016-11-01

    The ground state and excited state properties of three coumarin dyes, ZCJ1, ZCJ2 and ZCJ3, including ground state structures, energy levels, absorption spectra and driving forces of electron injection, were investigated via density functional theory (DFT) and time-dependent density functional theory (TD-DFT). In addition, five new molecules ZCJ3-1, ZCJ3-2, ZCJ3-3, ZCJ3-4 and ZCJ3-5 were designed through the introduction of a -CN group into molecule ZCJ3. The ground state and excited state properties of the five designed molecules were also calculated and compared with that of the original molecule, aiming to investigate the effect of different position of -CN groups on the optical and electrical properties of dye molecules. Moreover, the external electric field was taken into account. The results indicated that all three original molecules have better absorption within the visible-light range, and the molecule with a thiophene-thiophene conjugated bridge enables a red shift of the absorption spectrum. The molecule with a thiophene-benzene ring conjugated bridge enables the increase of driving force of electron injection. The energy levels, spectra and driving force of electron injection for the designed molecules are discussed in terms of studying their potential utility in dye-sensitized solar cells.

  9. Utilization of carboxylic functional groups generated during purification of carbon nanotube fiber for its strength improvement

    NASA Astrophysics Data System (ADS)

    Im, Yong-O.; Lee, Sung-Hyun; Kim, Teawon; Park, Junbeom; Lee, Jaegeun; Lee, Kun-Hong

    2017-01-01

    One of the most promising method to produce carbon nanotube (CNT) fiber is directly spinning CNT fiber from CNT aerogel. Despite the advantage of this method in terms of productivity, the CNTs thus produced include impurities such as amorphous carbon and residual catalysts. To remove these unwanted materials, the CNT fiber is usually subjected to acid treatment. At the same time, however, the acid treatment damages the CNT wall, creating functional groups on it. In this work, specific tensile strength of CNT fibers was increased by introducing cross-links between the individual CNTs using carboxylic functional groups which were inevitably generated during the acid treatment of CNT fibers. The esterification of the carboxylic acid with 1,5-pentanediol as a linker resulted in cross-links in between the CNTs, thereby increasing the specific strength of the CNT fiber from 0.43 to 1.12 N/tex and Young's modulus from 30.70 to 47.57 N/tex. Supporting weak shear interactions of untreated CNT fiber by adding covalent bonding through the cross-linking reaction led to the improvement of mechanical properties of the CNT fiber. Elimination of impurities and narrowed interspacing between CNT bundles caused by acid treatment was also confirmed, which additionally contributed to enhancing the mechanical properties of CNT fiber.

  10. Structure and function studies on enzymes with a catalytic carboxyl group(s): from ribonuclease T1 to carboxyl peptidases

    PubMed Central

    TAKAHASHI, Kenji

    2013-01-01

    A group of enzymes, mostly hydrolases or certain transferases, utilize one or a few side-chain carboxyl groups of Asp and/or Glu as part of the catalytic machinery at their active sites. This review follows mainly the trail of studies performed by the author and his colleagues on the structure and function of such enzymes, starting from ribonuclease T1, then extending to three major types of carboxyl peptidases including aspartic peptidases, glutamic peptidases and serine-carboxyl peptidases. PMID:23759941

  11. Social Skills Group Training in High-Functioning Autism: A Qualitative Responder Study

    ERIC Educational Resources Information Center

    Choque Olsson, Nora; Rautio, Daniel; Asztalos, Jenny; Stoetzer, Ulrich; Bölte, Sven

    2016-01-01

    Systematic reviews show some evidence for the efficacy of group-based social skills group training in children and adolescents with autism spectrum disorder, but more rigorous research is needed to endorse generalizability. In addition, little is known about the perspectives of autistic individuals participating in social skills group training.…

  12. Polar Addition to C=C Group: Why Is Anti-Markovnikov Hydroboration-Oxidation of Alkenes Not "Anti-"?

    ERIC Educational Resources Information Center

    Ilich, Predrag-Peter; Rickertsen, Lucas S.; Becker, Erienne

    2006-01-01

    For 137 years Markovnikov's rule has been extensively used in organic chemical education and research to describe the regioselectivity in electrophilic addition reactions to alkenes and alkynes. When the structures of the final reaction products are used as reference, the rule requests that certain polar addition reactions be termed…

  13. Role of oxygen functional groups in reduced graphene oxide for lubrication

    PubMed Central

    Gupta, Bhavana; Kumar, Niranjan; Panda, Kalpataru; Kanan, Vigneshwaran; Joshi, Shailesh; Visoly-Fisher, Iris

    2017-01-01

    Functionalized and fully characterized graphene-based lubricant additives are potential 2D materials for energy-efficient tribological applications in machine elements, especially at macroscopic contacts. Two different reduced graphene oxide (rGO) derivatives, terminated by hydroxyl and epoxy-hydroxyl groups, were prepared and blended with two different molecular weights of polyethylene glycol (PEG) for tribological investigation. Epoxy-hydroxyl-terminated rGO dispersed in PEG showed significantly smaller values of the friction coefficient. In this condition, PEG chains intercalate between the functionalized graphene sheets, and shear can take place between the PEG and rGO sheets. However, the friction coefficient was unaffected when hydroxyl-terminated rGO was coupled with PEG. This can be explained by the strong coupling between graphene sheets through hydroxyl units, causing the interaction of PEG with the rGO to be non- effective for lubrication. On the other hand, antiwear properties of hydroxyl-terminated rGO were significantly enhanced compared to epoxy-hydroxyl functionalized rGO due to the integrity of graphene sheet clusters. PMID:28344337

  14. Macroevolutionary trends of atomic composition and related functional group proportion in eukaryotic and prokaryotic proteins.

    PubMed

    Zhang, Yu-Juan; Yang, Chun-Lin; Hao, You-Jin; Li, Ying; Chen, Bin; Wen, Jian-Fan

    2014-01-25

    To fully explore the trends of atomic composition during the macroevolution from prokaryote to eukaryote, five atoms (oxygen, sulfur, nitrogen, carbon, hydrogen) and related functional groups in prokaryotic and eukaryotic proteins were surveyed and compared. Genome-wide analysis showed that eukaryotic proteins have more oxygen, sulfur and nitrogen atoms than prokaryotes do. Clusters of Orthologous Groups (COG) analysis revealed that oxygen, sulfur, carbon and hydrogen frequencies are higher in eukaryotic proteins than in their prokaryotic orthologs. Furthermore, functional group analysis demonstrated that eukaryotic proteins tend to have higher proportions of sulfhydryl, hydroxyl and acylamino, but lower of sulfide and carboxyl. Taken together, an apparent trend of increase was observed for oxygen and sulfur atoms in the macroevolution; the variation of oxygen and sulfur compositions and their related functional groups in macroevolution made eukaryotic proteins carry more useful functional groups. These results will be helpful for better understanding the functional significances of atomic composition evolution.

  15. Solvation free energy of the peptide group: its model dependence and implications for the additive-transfer free-energy model of protein stability.

    PubMed

    Tomar, Dheeraj S; Asthagiri, D; Weber, Valéry

    2013-09-17

    The group-additive decomposition of the unfolding free energy of a protein in an osmolyte solution relative to that in water poses a fundamental paradox: whereas the decomposition describes the experimental results rather well, theory suggests that a group-additive decomposition of free energies is, in general, not valid. In a step toward resolving this paradox, here we study the peptide-group transfer free energy. We calculate the vacuum-to-solvent (solvation) free energies of (Gly)n and cyclic diglycine (cGG) and analyze the data according to experimental protocol. The solvation free energies of (Gly)n are linear in n, suggesting group additivity. However, the slope interpreted as the free energy of a peptide unit differs from that for cGG scaled by a factor of half, emphasizing the context dependence of solvation. However, the water-to-osmolyte transfer free energies of the peptide unit are relatively independent of the peptide model, as observed experimentally. To understand these observations, a way to assess the contribution to the solvation free energy of solvent-mediated correlation between distinct groups is developed. We show that linearity of solvation free energy with n is a consequence of uniformity of the correlation contributions, with apparent group-additive behavior in the water-to-osmolyte transfer arising due to their cancellation. Implications for inferring molecular mechanisms of solvent effects on protein stability on the basis of the group-additive transfer model are suggested.

  16. Transformations and reactions of Re2(CO)8(mu-SbPh2)(mu-H) induced by the addition of a platinum(tri-t-butylphosphine) group.

    PubMed

    Adams, Richard D; Hall, Michael B; Pearl, William C; Yang, Xinzheng

    2009-01-19

    Three products Re(2)[Pt(PBu(t)(3))](mu-SbPh(2))(CO)(8)(mu-H), 2, Re(2)[Pt(CO)(PBu(t)(3))]Ph(CO)(8)(mu(3)-SbPh)(mu-H), 3, and Re(2)[Pt(PBu(t)(3))](2)(CO)(8)(mu(4)-Sb(2)Ph(2))(mu-H)(2), 4, were obtained from the reaction of Re(2)(CO)(8)(mu-SbPh(2))(mu-H), 1, with Pt(PBu(t)(3))(2). Compound 3 was also obtained from 2 by further reaction with Pt(PBu(t)(3))(2). Compound 2 is a Pt(PBu(t)(3)) adduct of 1 formed by the insertion of the platinum atom into one of the Re-Sb bonds of 1 with formation of two Pt-Re bonds. Compound 3 contains an open Re(2)Pt cluster and was also obtained in a low yield by the addition of CO to 2. The addition of SbPh(3) to 2 yielded the compound Re(2)Pt(PBu(t)(3))(Ph)(CO)(8)(SbPh(3))(mu(3)-SbPh)(mu-H), 5, a SbPh(3) derivative of 3. Compound 4 can be viewed as a dimer of the fragment Re[Pt(PBu(t)(3))](CO)(4)(SbPh)(mu-H). The two halves of the molecule are held together by Pt-Sb bonds and a significant interaction directly between the Sb atoms, Sb-Sb distance, 2.9834(7) A. The Sb-Sb bonding in 4 was explained by density functional calculations. Compound 4 adds 2 equiv of CO at 1 atm/25 degrees C, one to each platinum atom, to yield the compound [Re(CO)(4)Pt(H)(CO)(PBu(t)(3))(mu(3)-SbPh)](2) which exists as a mixture of two noninterconverting isomers, cis-6 and trans-6. Both isomers of 6 were isolated and structurally characterized. Each isomer of 6 consists of a central planar Re(2)Sb(2) core composed of two Re(CO)(4) groups with two bridging SbPh ligands. There is a Pt(H)(CO)(PBu(t)(3)) group coordinated to each antimony atom of 6. In the cis-isomer both Pt(H)(CO)(PBu(t)(3)) groups lie on the same side of the Re(2)Sb(2) plane. In the trans-isomer the Pt(H)(CO)(PBu(t)(3)) groups lie on opposite sides of the Re(2)Sb(2) plane.

  17. 14 CFR Section 10 - Functional Classification-Operating Expenses of Group I Air Carriers

    Code of Federal Regulations, 2010 CFR

    2010-01-01

    ... 14 Aeronautics and Space 4 2010-01-01 2010-01-01 false Functional Classification-Operating... REPORTS FOR LARGE CERTIFICATED AIR CARRIERS Profit and Loss Classification Section 10 Functional Classification—Operating Expenses of Group I Air Carriers 5100Flying Operations. (a) This function shall...

  18. Stereoselective synthesis of tricyclic compounds by intramolecular palladium-catalyzed addition of aryl iodides to carbonyl groups

    PubMed Central

    Saadi, Jakub; Bentz, Christoph; Redies, Kai; Lentz, Dieter; Zimmer, Reinhold

    2016-01-01

    Summary Starting from γ-ketoesters with an o-iodobenzyl group we studied a palladium-catalyzed cyclization process that stereoselectively led to bi- and tricyclic compounds in moderate to excellent yields. Four X-ray crystal structure analyses unequivocally defined the structure of crucial cyclization products. The relative configuration of the precursor compounds is essentially transferred to that of the products and the formed hydroxy group in the newly generated cyclohexane ring is consistently in trans-arrangement with respect to the methoxycarbonyl group. A transition-state model is proposed to explain the observed stereochemical outcome. This palladium-catalyzed Barbier-type reaction requires a reduction of palladium(II) back to palladium(0) which is apparently achieved by the present triethylamine. PMID:27559374

  19. Biogeographical Boundaries, Functional Group Structure and Diversity of Rocky Shore Communities along the Argentinean Coast

    PubMed Central

    Wieters, Evie A.; McQuaid, Christopher; Palomo, Gabriela; Pappalardo, Paula; Navarrete, Sergio A.

    2012-01-01

    We investigate the extent to which functional structure and spatial variability of intertidal communities coincide with major biogeographical boundaries, areas where extensive compositional changes in the biota are observed over a limited geographic extension. We then investigate whether spatial variation in the biomass of functional groups, over geographic (10′s km) and local (10′s m) scales, could be associated to species diversity within and among these groups. Functional community structure expressed as abundance (density, cover and biomass) and composition of major functional groups was quantified through field surveys at 20 rocky intertidal shores spanning six degrees of latitude along the southwest Atlantic coast of Argentina and extending across the boundaries between the Argentinean and Magellanic Provinces. Patterns of abundance of individual functional groups were not uniformly matched with biogeographical regions. Only ephemeral algae showed an abrupt geographical discontinuity coincident with changes in biogeographic boundaries, and this was limited to the mid intertidal zone. We identified 3–4 main ‘groups’ of sites in terms of the total and relative abundance of the major functional groups, but these did not coincide with biogeographical boundaries, nor did they follow latitudinal arrangement. Thus, processes that determine the functional structure of these intertidal communities are insensitive to biogeographical boundaries. Over both geographical and local spatial scales, and for most functional groups and tidal levels, increases in species richness within the functional group was significantly associated to increased total biomass and reduced spatial variability of the group. These results suggest that species belonging to the same functional group are sufficiently uncorrelated over space (i.e. metres and site-to-site ) to stabilize patterns of biomass variability and, in this manner, provide a buffer, or “insurance”, against spatial

  20. Succession of phytoplankton functional groups regulated by monsoonal hydrology in a large canyon-shaped reservoir.

    PubMed

    Xiao, Li-Juan; Wang, Tian; Hu, Ren; Han, Bo-Ping; Wang, Sheng; Qian, Xin; Padisák, Judit

    2011-10-15

    Liuxihe reservoir is a deep, monomictic, oligo-mesotrophic canyon-reservoir in the subtropical monsoon climate region of southern China. Phytoplankton functional groups in the reservoir were investigated and a comparison made between the succession observed in 2008, an exceptionally wet year, and 2009, an average year. The reservoir shows strong annual fluctuations in water level caused by monsoon rains and artificial drawdown. Altogether 28 functional groups of phytoplankton were identified, including 79 genera. Twelve of the groups were analyzed in detail using redundancy analysis. Because of the oligo-mesotrophic and P-limited condition of the reservoir, the dominant functional groups were those tolerant of nutrient (phosphorus) deficiency. The predominant functional groups in the succession process were Groups A (Cyclotella with greatest axial linear dimension<10 μm), B (Cyclotella with greatest axial linear dimension>10 μm), LO (Peridinium), LM (Ceratium and Microcystis), E (Dinobryon and Mallomonas), F (Botryococcus), X1 (Ankistrodesmus, Ankyra, Chlorella and Monoraphidium) and X2 (Chlamydomonas and Chroomonas). The development of groups A, B and LO was remarkably seasonal. Group A was dominant during stratification, when characteristic small size and high surface/volume ratio morphology conferred an advantage. Group LO was dominant during dry stratification, when motility was advantageous. Group B plankton exhibited a high relative biomass during periods of reduced euphotic depth and isothermy. Groups LM, E, F, X1 and X2 occasionally exhibited high relative biomasses attributable to specific environmental events (e.g. drawdown, changes in zooplankton community). A greater diversity of phytoplankton functional groups was apparent during isothermy. This study underscores the usefulness of functional algal groups in studying succession in subtropical impoundments, in which phytoplankton succession can be significantly affected by external factors such as

  1. Interactions Between Odorant Functional Group and Hydrocarbon Structure Influence Activity in Glomerular Response Modules in the Rat Olfactory Bulb

    PubMed Central

    Johnson, Brett A.; Farahbod, Haleh; Leon, Michael

    2008-01-01

    To investigate the effect of odorant hydrocarbon structure on spatial representations in the olfactory bulb systematically, we exposed rats to odorant chemicals possessing one of four different oxygen-containing functional groups on one of five different hydrocarbon backbones. We also used several hydrocarbon odorants lacking other functional groups. Hydrocarbon structural categories included straight-chained, branched, double-bonded, alicyclic, and aromatic features. Activity throughout the entire glomerular layer was measured as uptake of [14C]2-deoxyglucose and was mapped into anatomically standardized data matrices for statistical comparisons across different animals. Patterns evoked by straight-chained aliphatic odorants confirmed an association of activity in particular glomerular response modules with particular functional groups. However, the amount of activity in these same modules also was affected significantly by differences in hydrocarbon structure. Thus, the molecular features recognized by receptors projecting to these response modules appear to involve both functional group and hydrocarbon structural elements. In addition, particular benzyl and cyclohexyl odorants evoked activity in dorsal modules previously associated with the ketone functional group, which represents an exception to the rule of one feature per response module that had emerged from our previous studies. These dorsal modules also responded to nitrogen-containing aromatic compounds involving pyridine and pyrazine rings. The unexpected overlap in modular responses to ketones and odorants seemingly unrelated to ketones may reflect some covert shared molecular feature, the existence of odorant sensory neurons with multiple specificities, or a mosaic of sensory neuron projections to these particular modules. PMID:15678471

  2. Facile fabrication of siloxane @ poly (methylacrylic acid) core-shell microparticles with different functional groups

    NASA Astrophysics Data System (ADS)

    Zhao, Zheng-Bai; Tai, Li; Zhang, Da-Ming; Jiang, Yong

    2017-02-01

    Siloxane @ poly (methylacrylic acid) core-shell microparticles with functional groups were prepared by a facile hydrolysis-condensation method in this work. Three different silane coupling agents 3-methacryloxypropyltrimethoxysilane (MPS), 3-triethoxysilylpropylamine (APTES), and 3-glycidoxypropyltrimethoxysilane (GPTMS) were added along with tetraethoxysilane (TEOS) into the polymethylacrylic acid (PMAA) microparticle ethanol dispersion to form the Si@PMAA core-shell microparticles with different functional groups. The core-shell structure and the surface special functional groups of the resulting microparticles were measured by transmission electron microscopy and FTIR. The sizes of these core-shell microparticles were about 350-400 nm. The corresponding preparation conditions and mechanism were discussed in detail. This hydrolysis-condensation method also could be used to functionalize other microparticles which contain active groups on the surface. Meanwhile, the Si@PMAA core-shell microparticles with carbon-carbon double bonds and amino groups have further been applied to prepare hydrophobic coatings.

  3. Variation of phytoplankton functional groups modulated by hydraulic controls in Hongze Lake, China.

    PubMed

    Tian, Chang; Pei, Haiyan; Hu, Wenrong; Hao, Daping; Doblin, Martina A; Ren, Ying; Wei, Jielin; Feng, Yawei

    2015-11-01

    Hongze Lake is a large, shallow, polymictic, eutrophic lake in the eastern China. Phytoplankton functional groups in this lake were investigated from March 2011 to February 2013, and a comparison was made between the eastern, western, and northern regions. The lake shows strong fluctuations in water level caused by monsoon rains and regular hydraulic controls. By application of the phytoplankton functional group approach, this study aims to investigate the spatial and temporal dynamics and analyze their influencing factors. Altogether, 18 functional groups of phytoplankton were identified, encompassing 187 species. In order to seek the best variable describing the phytoplankton functional group distribution, 14 of the groups were analyzed in detail using redundancy analysis. Due to the turbid condition of the lake, the dominant functional groups were those tolerant of low light. The predominant functional groups in the annual succession were D (Cyclotella spp. and Synedra acus), T (Planctonema lauterbornii), P (Fragilaria crotonensis), X1 (Chlorella vulgaris and Chlorella pyrenoidosa), C (Cyclotella meneghiniana and Cyclotella ocellata), and Y (Cryptomonas erosa). An opposite relationship between water level and the biomass of predominant groups was observed in the present study. Water level fluctuations, caused by monsoonal climate and artificial drawdown, were significant factors influencing phytoplankton succession in Hongze Lake, since they alter the hydrological conditions and influence light and nutrient availability. The clearly demonstrated factors, which significantly influence phytoplankton dynamics in Hongze Lake, will help government manage the large shallow lakes with frequent water level fluctuations.

  4. Remote sulfonamido group enhances reactivity and selectivity for asymmetric Michael addition of nitroalkanes to α,β-unsaturated aldehydes.

    PubMed

    Huang, Yu-Chao; Uang, Biing-Jiun

    2014-09-01

    The pyrrolidine-camphorsulfonamide-based catalyst 1 a catalyzes the enantioselective conjugate addition of nitroalkanes to α,β-unsaturated aldehydes in the presence of five equivalents of water in iPrOH to give the corresponding chiral Michael adducts in good yields and high enantioselectivities (up to 99% ee) with a catalyst loading as low as 1 mol%.

  5. Redundancy and response diversity of functional groups: implications for the resilience of coral reefs.

    PubMed

    Nyström, Magnus

    2006-02-01

    To improve coral reef management, a deeper understanding of biodiversity across scales in the context of functional groups is required. The focus of this paper is on the role of diversity within functional groups in securing important ecosystem processes that contribute to the resilience of coral-dominated reef states. Two important components of species biodiversity that confer ecosystem resilience are analyzed: redundancy and the diversity of responses within functional groups to change. Three critical functional groups are used to illustrate the interaction between these two components and their role in coral reef resilience: zooxanthellae (symbiotic micro algae in reef-building corals), reef-building corals, and herbivores. The paper further examines the consequences of undermining functional redundancy and response diversity and addresses strategies to secure ecological processes that are critical for coral reef resilience.

  6. Preparation and characterization of an antibacterial ultrafiltration membrane with N-chloramine functional groups.

    PubMed

    Hou, Shuhua; Dong, Xue; Zhu, Jianhua; Zheng, Jifu; Bi, Weihui; Li, Shenghai; Zhang, Suobo

    2017-06-15

    In this study, a cardo poly(aryl ether ketone) ultrafiltration membrane containing an N-chloramine functional group (PEK-N-Cl membrane) was easily obtained via exposure of a cardo poly(aryl ether ketone) ultrafiltration membrane (PEK-NH membrane) to dilute sodium hypochlorite solution. The chlorination process did not harm membrane performance. In addition, the PEK-N-Cl membrane was stable in both air and water. The PEK-N-Cl membrane exhibited excellent antimicrobial properties against both Gram-negative and Gram-positive bacteria (i.e. E. coli and Bacillus subtilis, respectively). The PEK-N-Cl membrane provided 94.2% and 100% reduction of E. coli and Bacillus subtilis, respectively, within 30min of contact times. Moreover, nearly 100% of the E. coli was killed after 2h during the filtration process for the PEK-N-Cl membrane. In addition, the water flux decreased by 42% for the PEK-N-Cl membrane compared to 77.6% for the PEK-NH membrane after filtration of the E. coli solution and incubation on LB nutrient agar plate, indicating that the PEK-N-Cl membrane enhibits antifouling. Furthermore, the PEK-N-Cl membrane is recyclable via subsequent exposure to a sodium hypochlorite solution.

  7. A first principle study of graphene functionalized with hydroxyl, nitrile, or methyl groups

    NASA Astrophysics Data System (ADS)

    Barhoumi, M.; Rocca, D.; Said, M.; Lebègue, S.

    2017-01-01

    By means of ab initio calculations, we study the functionalization of graphene by different chemical groups such as hydroxyl, nitrile, or methyl. Two extreme cases of functionalization are considered: a single group on a supercell of graphene and a sheet of graphene fully functionalized. Once the equilibrium geometry is obtained by density functional theory, we found that the systems are metallic when a single group is attached to the sheet of graphene. With the exception of the nitrile functionalized boat configuration, a large bandgap is obtained at full coverage. Specifically, by using the GW approximation, our calculated bandgaps are direct and range between 5.0 and 5.5 eV for different configurations of hydroxyl functionalized graphene. An indirect GW bandgap of 6.50 eV was found in nitrile functionalized graphene while the methyl group functionalization leads to a direct bandgap with a value of 4.50 eV. Since in the two limiting cases of minimal and full coverage, the electronic structure changes drastically from a metal to a wide bandgap semiconductor, a series of intermediate states might be expected by tuning the amount of functionalization with these different groups.

  8. The functional architectures of addition and subtraction: Network discovery using fMRI and DCM.

    PubMed

    Yang, Yang; Zhong, Ning; Friston, Karl; Imamura, Kazuyuki; Lu, Shengfu; Li, Mi; Zhou, Haiyan; Wang, Haiyuan; Li, Kuncheng; Hu, Bin

    2017-03-27

    The neuronal mechanisms underlying arithmetic calculations are not well understood but the differences between mental addition and subtraction could be particularly revealing. Using fMRI and dynamic causal modeling (DCM), this study aimed to identify the distinct neuronal architectures engaged by the cognitive processes of simple addition and subtraction. Our results revealed significantly greater activation during subtraction in regions along the dorsal pathway, including the left inferior frontal gyrus (IFG), middle portion of dorsolateral prefrontal cortex (mDLPFC), and supplementary motor area (SMA), compared with addition. Subsequent analysis of the underlying changes in connectivity - with DCM - revealed a common circuit processing basic (numeric) attributes and the retrieval of arithmetic facts. However, DCM showed that addition was more likely to engage (numeric) retrieval-based circuits in the left hemisphere, while subtraction tended to draw on (magnitude) processing in bilateral parietal cortex, especially the right intraparietal sulcus (IPS). Our findings endorse previous hypotheses about the differences in strategic implementation, dominant hemisphere, and the neuronal circuits underlying addition and subtraction. Moreover, for simple arithmetic, our connectivity results suggest that subtraction calls on more complex processing than addition: auxiliary phonological, visual, and motor processes, for representing numbers, were engaged by subtraction, relative to addition. Hum Brain Mapp, 2017. © 2017 Wiley Periodicals, Inc.

  9. Manipulation of lysozyme phase behavior by additives as function of conformational stability.

    PubMed

    Galm, Lara; Morgenstern, Josefine; Hubbuch, Jürgen

    2015-10-15

    Undesired protein aggregation in general and non-native protein aggregation in particular need to be inhibited during bio-pharmaceutical processing to ensure patient safety and to maintain product activity. In this work the potency of different additives, namely glycerol, PEG 1000, and glycine, to prevent lysozyme aggregation and selectively manipulate lysozyme phase behavior was investigated. The results revealed a strong pH dependency of the additive impact on lysozyme phase behavior, lysozyme solubility, crystal size and morphology. This work aims to link this pH dependent impact to a protein-specific parameter, the conformational stability of lysozyme. At pH 3 the addition of 10% (w/v) glycerol, 10% (w/v) PEG 1000, and 1 M glycine stabilized or destabilized lysozymes' native conformation resulting in a modified size of the crystallization area without influencing lysozyme solubility, crystal size and morphology. Addition of 1 M glycine even promoted non-native aggregation at pH 3 whereas addition of PEG 1000 completely inhibited non-native aggregation. At pH 5 the addition of 10% (w/v) glycerol, 10% (w/v) PEG 1000, and 1 M glycine did not influence lysozymes' native conformation, but strongly influenced the position of the crystallization area, lysozyme solubility, crystal size and morphology. The observed pH dependent impact of the additives could be linked to a differing lysozyme conformational stability in the binary systems without additives at pH 3 and pH 5. However, in any case lysozyme phase behavior could selectively be manipulated by addition of glycerol, PEG 1000 and glycine. Furthermore, at pH 5 crystal size and morphology could selectively be manipulated.

  10. The Use of Functional Communication Training without Additional Treatment Procedures in an Inclusive School Setting

    ERIC Educational Resources Information Center

    Casey, Sean D.; Merical, Cheryl L.

    2006-01-01

    Functional communication training (FCT) is an intervention frequently used for students with developmental disabilities to reduce problematic behaviors and to increase prosocial behaviors. This intervention appears to be very effective when the communication responses trained are matched to the function of the student's problematic behaviors. In…

  11. Oleyl group-functionalized insulating gate transistors for measuring extracellular pH of floating cells

    PubMed Central

    Imaizumi, Yuki; Goda, Tatsuro; Toya, Yutaro; Matsumoto, Akira; Miyahara, Yuji

    2016-01-01

    Abstract The extracellular ionic microenvironment has a close relationship to biological activities such as by cellular respiration, cancer development, and immune response. A system composed of ion-sensitive field-effect transistors (ISFET), cells, and program-controlled fluidics has enabled the acquisition of real-time information about the integrity of the cell membrane via pH measurement. Here we aimed to extend this system toward floating cells such as T lymphocytes for investigating complement activation and pharmacokinetics through alternations in the plasma membrane integrity. We functionalized the surface of tantalum oxide gate insulator of ISFET with oleyl-tethered phosphonic acid for interacting with the plasma membranes of floating cells without affecting the cell signaling. The surface modification was characterized by X-ray photoelectron spectroscopy and water contact angle measurements. The Nernst response of −37.8 mV/pH was obtained for the surface-modified ISFET at 37 °C. The oleyl group-functionalized gate insulator successfully captured Jurkat T cells in a fluidic condition without acute cytotoxicity. The system was able to record the time course of pH changes at the cells/ISFET interface during the process of instant addition and withdrawal of ammonium chloride. Further, the plasma membrane injury of floating cells after exposure by detergent Triton™ X-100 was successfully determined using the modified ISFET with enhanced sensitivity as compared with conventional hemolysis assays. PMID:27877886

  12. Data-driven visualization and group analysis of multichannel EEG coherence with functional units.

    PubMed

    ten Caat, Michael; Maurits, Natasha M; Roerdink, Jos B T M

    2008-01-01

    A typical data-driven visualization of electroencephalography (EEG) coherence is a graph layout, with vertices representing electrodes and edges representing significant coherences between electrode signals. A drawback of this layout is its visual clutter for multichannel EEG. To reduce clutter, we define a functional unit (FU) as a data-driven region of interest (ROI). An FU is a spatially connected set of electrodes recording pairwise significantly coherent signals, represented in the coherence graph by a spatially connected clique. Earlier we presented two methods to detect FUs: a maximal clique based (MCB) method (time complexity O(3n/3), with n being the number of vertices) and a more efficient watershed based (WB) method (time complexity O (n2 log n)). To reduce the potential over-segmentation of the WB method, we introduce here an improved WB (IWB) method (time complexity O(n2 log n)). The IWB method merges basins representing FUs during the segmentation if they are spatially connected and if their union is a clique. The WB and IWB methods are both up to a factor of 100,000 faster than the MCB method for a typical multichannel setting with 128 EEG channels, thus making interactive visualization of multichannel EEG coherence possible. Results show that considering the MCB method as the gold standard, the difference between IWB and MCB FU maps is smaller than between WB and MCB FU maps. We also introduce two novel group maps for data-driven group analysis as extensions of the IWB method. First, the group mean coherence map preserves dominant features from a collection of individual FU maps. Second, the group FU size map visualizes the average FU size per electrode across a collection of individual FU maps. Finally, we employ an extensive case study to evaluate the IWB FU map and the two new group maps for data-driven group analysis. Results, in accordance with the conventional findings, indicate differences in EEG coherence between younger and older adults

  13. a Renormalization Group Calculation of the Velocity - and Density-Density Correlation Functions.

    NASA Astrophysics Data System (ADS)

    Cowan, Mark Timothy

    The velocity-velocity correlation function of a free field theory is obtained. The renormalization group, along with a 4-varepsilon expansion, is then used to find the leading order behavior of the velocity-velocity correlation function for an interacting field theory in the high temperature phase near the critical point. The details of the calculation of the density-density correlation function for Hedgehogs, in the context of a free field theory, is presented next. Finally the renormalization group, along with a 4-varepsilon expansion, is used to find the leading order behavior of the density-density correlation function for Hedgehogs in an interacting field theory near the critical point.

  14. Chemical characteristic and functional properties of arenga starch-taro (Colocasia esculanta L.) flour noodle with turmeric extracts addition

    NASA Astrophysics Data System (ADS)

    Ervika Rahayu N., H.; Ariani, Dini; Miftakhussolikhah, E., Maharani P.; Yudi, P.

    2017-01-01

    Arenga starch-taro (Colocasia esculanta L.) flour noodle is an alternative carbohydrate source made from 75% arenga starch and 25% taro flour, but it has a different color with commercial noodle product. The addition of natural color from turmeric may change the consumer preference and affect chemical characteristic and functional properties of noodle. This research aims to identify chemical characteristic and functional properties of arenga starch-taro flour noodle with turmeric extract addition. Extraction was performed using 5 variances of turmeric rhizome (0.06; 0.12; 0.18; 0.24; and 0.30 g (fresh weight/ml water). Then, noodle was made and chemical characteristic (proximate analysis) as well as functional properties (amylose, resistant starch, dietary fiber, antioxidant activity) were then evaluated. The result showed that addition of turmeric extract did not change protein, fat, carbohydrate, amylose, and resistant starch content significantly, while antioxidant activity was increased (23,41%) with addition of turmeric extract.

  15. [Decomposition of hemoglobin UV absorption spectrum into absorption spectra of prosthetic group and apoprotein by means of an additive model].

    PubMed

    Lavrinenko, I A; Vashanov, G A; Artyukhov, V G

    2015-01-01

    The decomposition pathways of hemoglobin UV absorption spectrum into the absorption spectra of the protein and non-protein components are proposed and substantiated by means of an additive model. We have established that the heme component has an absorption band with a maximum at λ(max) = 269.2 nm (ε = 97163) and the apoprotein component has an absorption band with a maximum at λ(max) = 278.4 nm (ε = 48669) for the wavelength range from 240.0 to 320.0 nm. An integral relative proportion of absorption for the heme fraction (78.8%) and apoprotein (21.2%) in the investigating wavelength range is defined.

  16. Functional response of osteoblasts in functionally gradient titanium alloy mesh arrays processed by 3D additive manufacturing.

    PubMed

    Nune, K C; Kumar, A; Misra, R D K; Li, S J; Hao, Y L; Yang, R

    2017-02-01

    We elucidate here the osteoblasts functions and cellular activity in 3D printed interconnected porous architecture of functionally gradient Ti-6Al-4V alloy mesh structures in terms of cell proliferation and growth, distribution of cell nuclei, synthesis of proteins (actin, vinculin, and fibronectin), and calcium deposition. Cell culture studies with pre-osteoblasts indicated that the interconnected porous architecture of functionally gradient mesh arrays was conducive to osteoblast functions. However, there were statistically significant differences in the cellular response depending on the pore size in the functionally gradient structure. The interconnected porous architecture contributed to the distribution of cells from the large pore size (G1) to the small pore size (G3), with consequent synthesis of extracellular matrix and calcium precipitation. The gradient mesh structure significantly impacted cell adhesion and influenced the proliferation stage, such that there was high distribution of cells on struts of the gradient mesh structure. Actin and vinculin showed a significant difference in normalized expression level of protein per cell, which was absent in the case of fibronectin. Osteoblasts present on mesh struts formed a confluent sheet, bridging the pores through numerous cytoplasmic extensions. The gradient mesh structure fabricated by electron beam melting was explored to obtain fundamental insights on cellular activity with respect to osteoblast functions.

  17. Controlling surface functionality through generation of thiol groups in a self-assembled monolayer.

    SciTech Connect

    Lud, S. Q.; Neppl, S.; Richter, G.; Bruno, P.; Gruen, D. M.; Jordan, R.; Feulner, P.; Stutzmann, M.; Garrido, J. A.; Materials Science Division; Technische Univ. Munchen

    2010-01-01

    A lithographic method to generate reactive thiol groups on functionalized synthetic diamond for biosensor and molecular electronic applications is developed. We demonstrate that ultrananocrystalline diamond (UNCD) thin films covalently functionalized with surface-generated thiol groups allow controlled thiol-disulfide exchange surface hybridization processes. The generation of the thiol functional head groups was obtained by irradiating phenylsulfonic acid (PSA) monolayers on UNCD surfaces. The conversion of the functional headgroup of the self-assembled monolayer was verified by using X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure (NEXAFS), and fluorescence microscopy. Our findings indicate the selective generation of reactive thiol surface groups. Furthermore, we demonstrate the grafting of yeast cytochrome c to the thiol-modified diamond surface and the electron transfer between protein and electrode.

  18. Illustrating the Use of Nonparametric Regression To Assess Differential Item and Bundle Functioning among Multiple Groups.

    ERIC Educational Resources Information Center

    Gierl, Mark J.; Bolt, Daniel M.

    2001-01-01

    Presents an overview of nonparametric regression as it allies to differential item functioning analysis and then provides three examples to illustrate how nonparametric regression can be applied to multilingual, multicultural data to study group differences. (SLD)

  19. Learning and Recovering Additive and Multiplicative Value Functions: A Criterion Validation of Multiattribute Utility Techniques

    DTIC Science & Technology

    1982-12-01

    multiattribute value functions. Operations Research, 1979, 27, 810-822. Fishburn, P. Utility theory for decision making. New York: Wiley, 1970...Psychology, 1980, 21, 66-82. v. Winterfeldt, D. and Fischer, G.W. Multiattribute utility theory : models and assessment procedres. In D. Wendt and...plicative value functions: A criterion _____________ validation of multiattribute utility 6. 7EPPORMING ONG. RgPeR? NUgMBER techn iclues 82-1 AijWOR*JS

  20. Additional borehole geophysical logging at Waste Area Grouping 1 at Oak Ridge National Laboratory, Oak Ridge, Tennessee

    SciTech Connect

    Not Available

    1994-07-01

    This technical memorandum describes the borehole geophysical logging performed at selected coreholes at Waste Area Grouping 1 between March and November 1991 in support of the remedial investigation. The primary objectives of the borehole geophysical logging program were to (1) identify fractured bedrock zones and identify those fractured bedrock zones participating in active groundwater flow, (2) correlate the fractured intervals with the regional stratigraphy described, and (3) further characterize local bedrock geology and hydrogeology and gain insight about the bedrock aquifer flow system. A secondary objective was to provide stratigraphic correlations with existing logs for coreholes CH001 through CH005. Fractured bedrock zones and active or open fractures were identified in all coreholes logged. The fracture identification and analysis process was intended to distinguish between open or active fractures participating in active groundwater flow and closed or inactive fractures that are partially or completely filled (such as with calcite mineralization) and do not support groundwater circulation. Most of the fractures identified are bedding plane. Fracture occurrence varies with the different units of the Chickamauga Group; the greatest density of fractures and active fractures occurs in the upper 150 ft of stratum cored. Fractures actively contributing to groundwater flow were also identified, and direction of fluid movement within fractures was identified for those coreholes with flowmeter data.

  1. Changes of soil bacterial activities and functions after different N additions in a temperate forest.

    PubMed

    Guo, Peng; Han, Tiwen; Zhang, Li; Li, Shushan; Ma, Dongzhu; Du, Yuhan

    2017-02-01

    It has been shown that different nitrogen (N) addition led to various influences on soil microbial activities in forest ecosystems; however, the changes of bacteria were still unclear. In this work, inorganic N (NH4NO3) and organic N (urea and glycine) were fertilized with different ratios (5:0, 1:4, 3:2, 2:3, and 1:4) on temperate forest soils, while fungicide (cycloheximide) was simultaneously added on half of each treatment to inhibit fungal activities (leaving only bacteria). After a 3-year field experiment, soil samples were harvested, then microbial enzymatic activities involved in carbon (C), and N and phosphorus (P) cycles were determined. Under laboratory conditions, four purified bacteria which were isolated from sample site had been inoculated in sterilized soils under different N types and enzymatic activities were assayed after 90-day incubation. The results showed that cellulase and polyphenol oxidase activities of non-fungicide-added treatments increased after N addition and greater organic N accelerated the increases. However, these enzymatic activities of fungicide-added treatments were not significantly influenced by N addition and N types. It may be due to the insufficient ability of bacteria to synthesize enough enzymes to decompose complex organic C (such as cellulose and lignin) into available compound, although N-limitation was alleviated. Alkaline phosphatase activities increased after N addition in both non-fungicide-added and fungicide-added treatments, and the acceleration on bacterial alkaline phosphatase activities was even greater. Furthermore, organic N showed at least 2.5 times promotion on bacteria alkaline phosphatase than those of inorganic N, which indicated greater alleviation of bacterial P-limitation after the addition of organic N. All the results indicated that soil bacteria may be seriously limited by soil available C but become the dominant decomposer of the complex P compounds after N addition, particularly greater

  2. Functional group placement in protein binding sites: a comparison of GRID and MCSS

    NASA Astrophysics Data System (ADS)

    Bitetti-Putzer, Ryan; Joseph-McCarthy, Diane; Hogle, James M.; Karplus, Martin

    2001-10-01

    One approach to combinatorial ligand design begins by determining optimal locations (i.e., local potential energy minima) for functional groups in the binding site of a target macromolecule. MCSS and GRID are two methods, based on significantly different algorithms, which are used for this purpose. A comparison of the two methods for the same functional groups is reported. Calculations were performed for nonpolar and polar functional groups in the internal hydrophobic pocket of the poliovirus capsid protein, and on the binding surface of the src SH3 domain. The two approaches are shown to agree qualitatively; i.e., the global characteristics of the functional group maps generated by MCSS and GRID are similar. However, there are significant differences in the relative interaction energies of the two sets of minima, a consequence of the different functional form used to evaluate polar interactions (electrostatics and hydrogen bonding) in the two methods. The single sphere representation used by GRID affords only positional information, supplemented by the identification of hydrogen bonding interactions. By contrast, the multi-atom representation of most MCSS groups yields in both positional and orientational information. The two methods are most similar for small functional groups, while for larger functional groups MCSS yields results consistent with GRID but superior in detail. These results are in accord with the somewhat different purposes for which the two methods were developed. GRID has been used mainly to introduce functionalities at specific positions in lead compounds, in which case the orientation is predetermined by the structure of the latter. The orientational information provided by MCSS is important for its use in the de novo design of large, multi-functional ligands, as well as for improving lead compounds.

  3. How do Elevated CO2 and Nitrogen Addition Affect Functional Microbial Community Involved in Greenhouse Gas Flux in Salt Marsh System.

    PubMed

    Lee, Seung-Hoon; Megonigal, Patrick J; Kang, Hojeong

    2017-03-22

    Salt marshes are unique ecosystem of which a microbial community is expected to be affected by global climate change. In this study, by using T-RFLP analysis, quantitative PCR, and pyrosequencing, we comprehensively analyzed the microbial community structure responding to elevated CO2 (eCO2) and N addition in a salt marsh ecosystem subjected to CO2 manipulation and N addition for about 3 years. We focused on the genes of microbes relevant to N-cycling (denitrification and nitrification), CH4-flux (methanogens and methanotrophs), and S-cycling (sulfate reduction) considering that they are key functional groups involved in the nutrient cycle of salt marsh system. Overall, this study suggests that (1) eCO2 and N addition affect functional microbial community involved in greenhouse gas flux in salt marsh system. Specifically, the denitrification process may be facilitated, while the methanogenesis may be impeded due to the outcompeting of sulfate reduction by eCO2 and N. This implies that future global change may cause a probable change in GHGs flux and positive feedback to global climate change in salt marsh; (2) the effect of eCO2 and N on functional group seems specific and to contrast with each other, but the effect of single factor would not be compromised but complemented by combination of two factors. (3) The response of functional groups to eCO2 and/or N may be directly or indirectly related to the plant community and its response to eCO2 and/or N. This study provides new insights into our understanding of functional microbial community responses to eCO2 and/or N addition in a C3/C4 plant mixed salt marsh system.

  4. Density functional study of hydrogen bond formation between methanol and organic molecules containing Cl, F, NH2, OH, and COOH functional groups.

    PubMed

    Kolev, Stefan K; St Petkov, Petko; Rangelov, Miroslav A; Vayssilov, Georgi N

    2011-12-08

    Various hydrogen-bonded complexes of methanol with different proton accepting and proton donating molecules containing Cl, F, NH(2), OH, OR, and COOH functional groups have been modeled using DFT with hybrid B3LYP and M05-2X functionals. The latter functional was found to provide more accurate estimates of the structural and thermodynamic parameters of the complexes of halides, amines, and alcohols. The characteristics of these complexes are influenced not only by the principle hydrogen bond of the methanol OH with the proton acceptor heteroatom, but also by additional hydrogen bonds of a C-H moiety with methanol oxygen as a proton acceptor. The contribution of the former hydrogen bond in the total binding enthalpy increases in the order chlorides < fluorides < alcohols < amines, while the contribution of the second type of hydrogen bond increases in the reverse order. A general correlation was found between the binding enthalpy of the complex and the electrostatic potential at the hydrogen center participating in the formation of the hydrogen bond. The calculated binding enthalpies of different complexes were used to clarify which functional groups can potentially form a hydrogen bond to the 2'-OH hydroxyl group in ribose, which is strong enough to block it from participation in the intramolecular catalytic activation of the peptide bond synthesis. Such blocking could result in inhibition of the protein biosynthesis in the living cell if the corresponding group is delivered as a part of a drug molecule in the vicinity of the active site in the ribosome. According to our results, such activity can be accomplished by secondary or tertiary amines, alkoxy groups, deprotonated carboxyl groups, and aliphatic fluorides, but not by the other modeled functional groups.

  5. A Functional Group Approach for Prediction of APPI Response of Organic Synthetic Targets

    NASA Astrophysics Data System (ADS)

    Zhurov, Konstantin O.; Menin, Laure; Di Franco, Thomas; Tsybin, Yury O.

    2015-07-01

    Atmospheric pressure photoionization (APPI) is a technique of choice for ionization of non-polar molecules in mass spectrometry (MS). Reported APPI-based studies tend to focus on a selected compound class, which may contain a variety of functional groups. These studies demonstrate that APPI response frequently differs substantially, indicating a certain dependence on the functional group present. Although this dependence could be employed for APPI response prediction, its systematic use is currently absent. Here, we apply APPI MS to a judiciously-compiled set of 63 compounds containing a number of diverse functional groups commonly utilized in synthesis, reactive functional groups, as well as those containing boron and silicon. Based on the outcome of APPI MS of these compounds, we propose and evaluate a simple guideline to estimate the APPI response for a novel compound, the key properties of which have not been characterized in the gas phase. Briefly, we first identify key functional groups in the compound and gather knowledge on the known ionization energies from the smallest analogues containing said functional groups. We then consider local inductive and resonance effects on said ionization energies for the compounds of interest to estimate the APPI response. Finally, application of APPI MS to compounds of interest considered herein demonstrated extended upper mass ionization limit of 3.5 kDa for non-polymeric compounds.

  6. Multiple-Group Noncompensatory Differential Item Functioning in Raju's Differential Functioning of Items and Tests

    ERIC Educational Resources Information Center

    Oshima, T. C.; Wright, Keith; White, Nick

    2015-01-01

    Raju, van der Linden, and Fleer (1995) introduced a framework for differential functioning of items and tests (DFIT) for unidimensional dichotomous models. Since then, DFIT has been shown to be a quite versatile framework as it can handle polytomous as well as multidimensional models both at the item and test levels. However, DFIT is still limited…

  7. Identification of Differential Item Functioning in Multiple-Group Settings: A Multivariate Outlier Detection Approach

    ERIC Educational Resources Information Center

    Magis, David; De Boeck, Paul

    2011-01-01

    We focus on the identification of differential item functioning (DIF) when more than two groups of examinees are considered. We propose to consider items as elements of a multivariate space, where DIF items are outlying elements. Following this approach, the situation of multiple groups is a quite natural case. A robust statistics technique is…

  8. The Use of Language Functions in Mathematical Group Games. Teacher Insights.

    ERIC Educational Resources Information Center

    Black, Carolyn; Huerta, Maria G.

    1994-01-01

    Six group games were introduced into a second-grade bilingual classroom. Children's talk during each game was classified using a modification of Dyson's five language functions (representational, directive, heuristic, personal, and interactional). Group games provided many communication opportunities. Some children tried new communication styles.…

  9. Characteristics of Interactional Management Functions in Group Oral by Japanese Learners of English

    ERIC Educational Resources Information Center

    Negishi, Junko

    2010-01-01

    This study attempted to investigate the characteristics of interaction dynamics in a group oral interaction carried out by Japanese learners of English. The relationship between the participants' language development and interactional management functions (IMFs) was also explored. Oral performance tests in a paired or a small group have recently…

  10. Functional Groups Based on Leaf Physiology: Are they Spatially and Temporally Robust?

    NASA Technical Reports Server (NTRS)

    Foster, Tammy E.; Brooks, J. Renee

    2004-01-01

    The functional grouping hypothesis, which suggests that complexity in ecosystem function can be simplified by grouping species with similar responses, was tested in the Florida scrub habitat. Functional groups were identified based on how species in fire maintained Florida scrub regulate exchange of carbon and water with the atmosphere as indicated by both instantaneous gas exchange measurements and integrated measures of function (%N, delta C-13, delta N-15, C-N ratio). Using cluster analysis, five distinct physiologically-based functional groups were identified in the fire maintained scrub. These functional groups were tested to determine if they were robust spatially, temporally, and with management regime. Analysis of Similarities (ANOSIM), a non-parametric multivariate analysis, indicated that these five physiologically-based groupings were not altered by plot differences (R = -0.115, p = 0.893) or by the three different management regimes; prescribed burn, mechanically treated and burn, and fire-suppressed (R = 0.018, p = 0.349). The physiological groupings also remained robust between the two climatically different years 1999 and 2000 (R = -0.027, p = 0.725). Easy-to-measure morphological characteristics indicating functional groups would be more practical for scaling and modeling ecosystem processes than detailed gas-exchange measurements, therefore we tested a variety of morphological characteristics as functional indicators. A combination of non-parametric multivariate techniques (Hierarchical cluster analysis, non-metric Multi-Dimensional Scaling, and ANOSIM) were used to compare the ability of life form, leaf thickness, and specific leaf area classifications to identify the physiologically-based functional groups. Life form classifications (ANOSIM; R = 0.629, p 0.001) were able to depict the physiological groupings more adequately than either specific leaf area (ANOSIM; R = 0.426, p = 0.001) or leaf thickness (ANOSIM; R 0.344, p 0.001). The ability of

  11. Meaning and Function of Dummy Auxiliaries in Adult Acquisition of Dutch as an Additional Language

    ERIC Educational Resources Information Center

    Julien, Manuela; van Hout, Roeland; van de Craats, Ineke

    2016-01-01

    This article presents the results of experimental data on language production and comprehension. These show that adult learners of Dutch as an additional language, with different language backgrounds, and a L2 proficiency below level A2 (Waystage) of the Common European Framework of Reference for Languages (CEFR; Council of Europe, 2001), use…

  12. Molecular aspects of aromatic C additions to soils: Implications of biochar quality for ecosystem functionality

    EPA Science Inventory

    Solid residues of incomplete combustion (biochar or char) are continuously being added to soils due to natural vegetation fires in many ecosystems. However, new strategies for carbon sequestration in soils are likely to include the active addition of biochar to soils. Since bioc...

  13. Percolation galaxy groups and clusters in the sdss redshift survey: identification, catalogs, and the multiplicity function

    SciTech Connect

    Berlind, Andreas A.; Frieman, Joshua A.; Weinberg, David H.; Blanton, Michael R.; Warren, Michael S.; Abazajian, Kevork; Scranton, Ryan; Hogg, David W.; Scoccimarro, Roman; Bahcall, Neta A.; Brinkmann, J.; Gott, J.Richard, III; Kleinman, S.J.; Krzesinski, J.; Lee, Brian C.; Miller, Christopher J.; Nitta, Atsuko; Schneider, Donald P.; Tucker, Douglas L.; Zehavi, Idit; /CCPP, New York /Chicago U., Astron. Astrophys. Ctr. /Ohio State U., Dept. Astron. /Los Alamos /Pittsburgh U. /Princeton U. /Subaru Telescope /Apache Point Observ. /Mt. Suhora Observ., Cracow /LBL, Berkeley /Cerro-Tololo InterAmerican Obs. /Penn State U., Astron. Astrophys. /Fermilab /Arizona U., Astron. Dept. - Steward Observ. /Case Western Reserve U.

    2006-01-01

    We identify galaxy groups and clusters in volume-limited samples of the SDSS redshift survey, using a redshift-space friends-of-friends algorithm. We optimize the friends-of-friends linking lengths to recover galaxy systems that occupy the same dark matter halos, using a set of mock catalogs created by populating halos of N-body simulations with galaxies. Extensive tests with these mock catalogs show that no combination of perpendicular and line-of-sight linking lengths is able to yield groups and clusters that simultaneously recover the true halo multiplicity function, projected size distribution, and velocity dispersion. We adopt a linking length combination that yields, for galaxy groups with ten or more members: a group multiplicity function that is unbiased with respect to the true halo multiplicity function; an unbiased median relation between the multiplicities of groups and their associated halos; a spurious group fraction of less than {approx}1%; a halo completeness of more than {approx}97%; the correct projected size distribution as a function of multiplicity; and a velocity dispersion distribution that is {approx}20% too low at all multiplicities. These results hold over a range of mock catalogs that use different input recipes of populating halos with galaxies. We apply our group-finding algorithm to the SDSS data and obtain three group and cluster catalogs for three volume-limited samples that cover 3495.1 square degrees on the sky. We correct for incompleteness caused by fiber collisions and survey edges, and obtain measurements of the group multiplicity function, with errors calculated from realistic mock catalogs. These multiplicity function measurements provide a key constraint on the relation between galaxy populations and dark matter halos.

  14. Loop expansion of the average effective action in the functional renormalization group approach

    NASA Astrophysics Data System (ADS)

    Lavrov, Peter M.; Merzlikin, Boris S.

    2015-10-01

    We formulate a perturbation expansion for the effective action in a new approach to the functional renormalization group method based on the concept of composite fields for regulator functions being their most essential ingredients. We demonstrate explicitly the principal difference between the properties of effective actions in these two approaches existing already on the one-loop level in a simple gauge model.

  15. New method of the functional renormalization group approach for Yang-Mills fields

    NASA Astrophysics Data System (ADS)

    Lavrov, P. M.; Shapiro, I. L.

    2014-12-01

    We propose a new formulation of the functional renormalization group (FRG) approach, based on the use of regulator functions as composite operators. In this case one can provide (in contrast with standard approach) on-shell gauge-invariance for the effective average action.

  16. Addition of Functional Content during Core Content Instruction with Students with Moderate Disabilities

    ERIC Educational Resources Information Center

    Collins, Belva C.; Hager, Karen L.; Galloway, Carey Creech

    2011-01-01

    The purpose of this investigation was to add functional content during core content instruction of language arts, science, and math. The investigation involved three middle school students with moderate disabilities who participated in the state's alternate assessment. During instruction using a constant time delay procedure to teach required…

  17. Addition of azomethine ylides to C[sub 60]. Synthesis, characterization, and functionalization of fullerene pyrrolidines

    SciTech Connect

    Maggini, M.; Scorrano, G. ); Prato, M. )

    1993-10-20

    We report herein a new and very general fullerene functionalization, based on the 1,3-dipolar cycloaddition of azomethine ylides to C[sub 60]. Azomethine ylides, planar species of general formula (R[sup 1]R[sup 2])-C=N[sup +](R[sup 3]) - C[sup [minus

  18. Using Additional Analyses to Clarify the Functions of Problem Behavior: An Analysis of Two Cases

    ERIC Educational Resources Information Center

    Payne, Steven W.; Dozier, Claudia L.; Neidert, Pamela L.; Jowett, Erica S.; Newquist, Matthew H.

    2014-01-01

    Functional analyses (FA) have proven useful for identifying contingencies that influence problem behavior. Research has shown that some problem behavior may only occur in specific contexts or be influenced by multiple or idiosyncratic variables. When these contexts or sources of influence are not assessed in an FA, further assessment may be…

  19. Lung function decline rates according to GOLD group in patients with chronic obstructive pulmonary disease

    PubMed Central

    Kim, Joohae; Yoon, Ho Il; Oh, Yeon-Mok; Lim, Seong Yong; Lee, Ji-Hyun; Kim, Tae-Hyung; Lee, Sang Yeub; Lee, Jin Hwa; Lee, Sang-Do; Lee, Chang-Hoon

    2015-01-01

    Background Since the Global Initiative for Chronic Obstructive Lung Disease (GOLD) groups A–D were introduced, the lung function changes according to group have been evaluated rarely. Objective We investigated the rate of decline in annual lung function in patients categorized according to the 2014 GOLD guidelines. Methods Patients with COPD included in the Korean Obstructive Lung Disease (KOLD) prospective study, who underwent yearly postbronchodilator spirometry at least three times, were included. The main outcome was the annual decline in postbronchodilator forced expiratory volume in 1 second (FEV1), which was analyzed by random-slope and random-intercept mixed linear regression. Results A total 175 participants were included. No significant postbronchodilator FEV1 decline was observed between the groups (−34.4±7.9 [group A]; −26.2±9.4 [group B]; −22.7±16.0 [group C]; and −24.0±8.7 mL/year [group D]) (P=0.79). The group with less symptoms (−32.3±7.2 vs −25.0±6.5 mL/year) (P=0.44) and the low risk group (−31.0±6.1 vs −23.6±7.7 mL/year) (P=0.44) at baseline showed a more rapid decline in the postbronchodilator FEV1, but the trends were not statistically significant. However, GOLD stages classified by FEV1 were significantly related to the annual lung function decline. Conclusion There was no significant difference in lung function decline rates according to the GOLD groups. Prior classification using postbronchodilator FEV1 predicts decline in lung function better than does the new classification. PMID:26379432

  20. Three Additional Linkage Groups That Repress Transcription and Meiotic Recombination in the Mating-Type Region of Schizosaccharomyces Pombe

    PubMed Central

    Thon, G.; Cohen, A.; Klar, A. J.

    1994-01-01

    The mating-type genes of Schizosaccharomyces pombe are found at three locations in the same chromosomal region. These genes are in an active configuration at the mat1 locus and in an inactive configuration at the mat2 and mat3 loci. The mechanism that represses transcription of mat2 and mat3 also inactivates other promoters introduced nearby and is accompanied by a block to meiotic recombination in the mat2-mat3 interval, suggesting that this mechanism involves a particular chromatin structure. We present evidence that the transcription and recombination blocks require three newly defined trans-acting loci, clr2, clr3 and clr4, in addition to the previously identified clr1, rik1 and swi6 loci. We also investigated the role of mat2 cis-acting sequences in silencing. Four cis-acting elements that repress mat2 in a plasmid context were previously identified. Deletion of two of these elements proved to have little effect in a chromosomal context. However, when combined with mutations in trans-acting genes, deletion of the same two elements greatly enhanced mat2 expression. The observed cumulative effects suggest a redundancy in the silencing mechanism. PMID:8001791

  1. Soil surface protection by Biocrusts: effects of functional groups on textural properties

    NASA Astrophysics Data System (ADS)

    Concostrina-Zubiri, Laura; Huber-Sannwald, Elisabeth; Martínez, Isabel; Flores Flores, José Luis; Escudero, Adrián

    2015-04-01

    In drylands, where vegetation cover is commonly scarce, soil surface is prone to wind and water soil erosion, with the subsequent loss of topsoil structure and chemical properties. These processes are even more pronounced in ecosystems subjected to extra erosive forces, such as grasslands and rangelands that support livestock production. However, some of the physiological and functional traits of biocrusts (i.e., complex association of cyanobacteria, lichens, mosses, fungi and soil particles) make them ideal to resist in disturbed environments and at the same time to protect soil surface from mechanical perturbations. In particular, the filaments and exudates of soil cyanobacteria and the rhizines of lichen can bind together soil particles, forming soil aggregates at the soil surface and thus enhancing soil stability. Also, they act as "biological covers" that preserve the most vulnerable soil layer from wind and runoff erosion and raindrop impact, maintaining soil structure and composition. In this work, we evaluated soil textural properties and organic matter content under different functional groups of biocrusts (i.e., cyanobacteria crust, 3 lichen species, 1 moss species) and in bare soil. In order to assess the impact of livestock trampling on soil properties and on Biocrust function, we sampled three sites conforming a disturbance gradient (low, medium and high impact sites) and a long-term livestock exclusion as control site. We found that the presence of biocrusts had little effects on soil textural properties and organic matter content in the control site, while noticeable differences were found between bare soil and soil under biocrusts (e.g., up to 16-37% higher clay content, compared to bare soil and up to 10% higher organic matter content). In addition, we found that depending on morphological traits and grazing regime, the effects of biocrusts changed along the gradient. For example, soil under the lichen Diploschistes diacapsis, with thick thallus

  2. Organocatalyzed cascade aza-Michael/Michael addition for the asymmetric construction of highly functionalized spiropyrazolone tetrahydroquinolines.

    PubMed

    Li, Jun-Hua; Du, Da-Ming

    2014-11-01

    An organocatalyzed diastereo- and enantioselective cascade aza-Michael/Michael addition of 2-tosylaminoenones to unsaturated pyrazolones has been developed to afford novel chiral spiropyrazolone tetrahydroquinolines containing three contiguous stereocenters. This cascade reaction proceeded well with 2 mol% chiral bifunctional tertiary amine squaramide catalyst to give the desired products in excellent yields (up to 99%) with excellent diastereoselectivity (up to >25:1 diastereomeric ratio) and high enantioselectivity (up to 91% enantiomeric excess).

  3. Metal-Catalyzed β-Functionalization of Michael Acceptors through Reductive Radical Addition Reactions.

    PubMed

    Streuff, Jan; Gansäuer, Andreas

    2015-11-23

    Transition-metal-catalyzed radical reactions are becoming increasingly important in modern organic chemistry. They offer fascinating and unconventional ways for connecting molecular fragments that are often complementary to traditional methods. In particular, reductive radical additions to α,β-unsaturated compounds have recently gained substantial attention as a result of their broad applicability in organic synthesis. This Minireview critically discusses the recent landmark achievements in this field in context with earlier reports that laid the foundation for today's developments.

  4. Effects of resource addition on recovery of production and plant functional composition in degraded semiarid grasslands.

    PubMed

    Chen, Qing; Hooper, David U; Li, Hui; Gong, Xiao Ying; Peng, Fei; Wang, Hong; Dittert, Klaus; Lin, Shan

    2017-02-28

    Degradation of semiarid ecosystems from overgrazing threatens a variety of ecosystem services. Rainfall and nitrogen commonly co-limit production in semiarid grassland ecosystems; however, few studies have reported how interactive effects of precipitation and nitrogen addition influence the recovery of grasslands degraded by overgrazing. We conducted a 6-year experiment manipulating precipitation (natural precipitation and simulated wet year precipitation) and nitrogen (0, 25 and 50 kg N ha(-1)) addition at two sites with different histories of livestock grazing (moderately and heavily grazed) in Inner Mongolian steppe. Our results suggest that recovery of plant community composition and recovery of production can be decoupled. Perennial grasses provide long-term stability of high-quality forage production in this system. Supplemental water combined with exclosures led, in the heavily grazed site, to the strongest recovery of perennial grasses, although widespread irrigation of rangeland is not a feasible management strategy in many semiarid and arid regions. N fertilization combined with exclosures, but without water addition, increased dominance of unpalatable annual species, which in turn retarded growth of perennial species and increased inter-annual variation in primary production at both sites. Alleviation of grazing pressure alone allowed recovery of desired perennial species via successional processes in the heavily grazed site. Our experiments suggest that recovery of primary production and desirable community composition are not necessarily correlated. The use of N fertilization for the management of overgrazed grassland needs careful and systematic evaluation, as it has potential to impede, rather than aid, recovery.

  5. Functional specialization and generalization for grouping of stimuli based on colour and motion

    PubMed Central

    Zeki, Semir; Stutters, Jonathan

    2013-01-01

    This study was undertaken to learn whether the principle of functional specialization that is evident at the level of the prestriate visual cortex extends to areas that are involved in grouping visual stimuli according to attribute, and specifically according to colour and motion. Subjects viewed, in an fMRI scanner, visual stimuli composed of moving dots, which could be either coloured or achromatic; in some stimuli the moving coloured dots were randomly distributed or moved in random directions; in others, some of the moving dots were grouped together according to colour or to direction of motion, with the number of groupings varying from 1 to 3. Increased activation was observed in area V4 in response to colour grouping and in V5 in response to motion grouping while both groupings led to activity in separate though contiguous compartments within the intraparietal cortex. The activity in all the above areas was parametrically related to the number of groupings, as was the prominent activity in Crus I of the cerebellum where the activity resulting from the two types of grouping overlapped. This suggests (a) that, the specialized visual areas of the prestriate cortex have functions beyond the processing of visual signals according to attribute, namely that of grouping signals according to colour (V4) or motion (V5); (b) that the functional separation evident in visual cortical areas devoted to motion and colour, respectively, is maintained at the level of parietal cortex, at least as far as grouping according to attribute is concerned; and (c) that, by contrast, this grouping-related functional segregation is not maintained at the level of the cerebellum. PMID:23415950

  6. Classifying proteins into functional groups based on all-versus-all BLAST of 10 million proteins.

    PubMed

    Kolker, Natali; Higdon, Roger; Broomall, William; Stanberry, Larissa; Welch, Dean; Lu, Wei; Haynes, Winston; Barga, Roger; Kolker, Eugene

    2011-01-01

    To address the monumental challenge of assigning function to millions of sequenced proteins, we completed the first of a kind all-versus-all sequence alignments using BLAST for 9.9 million proteins in the UniRef100 database. Microsoft Windows Azure produced over 3 billion filtered records in 6 days using 475 eight-core virtual machines. Protein classification into functional groups was then performed using Hive and custom jars implemented on top of Apache Hadoop utilizing the MapReduce paradigm. First, using the Clusters of Orthologous Genes (COG) database, a length normalized bit score (LNBS) was determined to be the best similarity measure for classification of proteins. LNBS achieved sensitivity and specificity of 98% each. Second, out of 5.1 million bacterial proteins, about two-thirds were assigned to significantly extended COG groups, encompassing 30 times more assigned proteins. Third, the remaining proteins were classified into protein functional groups using an innovative implementation of a single-linkage algorithm on an in-house Hadoop compute cluster. This implementation significantly reduces the run time for nonindexed queries and optimizes efficient clustering on a large scale. The performance was also verified on Amazon Elastic MapReduce. This clustering assigned nearly 2 million proteins to approximately half a million different functional groups. A similar approach was applied to classify 2.8 million eukaryotic sequences resulting in over 1 million proteins being assign to existing KOG groups and the remainder clustered into 100,000 functional groups.

  7. The impact of functional group on the electronic structure of coordination center

    NASA Astrophysics Data System (ADS)

    Hooshmand Gharehbagh, Zahra; L, Duy; Rahman, Talat S.

    While 9, 10 dicyano-anthracene (DCA) forms a coordination network on Cu(111) surface with Cu adatom coordinated by three DCA molecules, its isomers, 9,10-diisocyano-anthracene forms, surprisingly, molecular rows on the same surface. To understand the impact of functional groups on the electronic structure of the coordination center, we have carried out density functional theory based calculations of the electronic structure of a set of naphthalene molecules with different functional groups (N, CN, NC, NH2, COH, COOH) adsorbed on Cu(111), with and without a Cu adatom. Our results show that while the interaction between the naphthalene backbone and the Cu(111) surface is dominated by van der Waals (vdW) forces, in all cases considered the functional group forms a covalent bond with the Cu (ad)atom (on) of the surface. The calculated differential charge redistribution shows that the strongest covalent bond is formed by the NC group, which differs remarkably from that formed by the CN group, while the vdW interaction is very similar in both cases. These results provide insights into the different surface coordination behavior of molecules with above-mentioned functional groups. Work support in part by NSF Grant CHE-1310327.

  8. Clickable SBA-15 to screen functional groups for adsorption of antibiotics.

    PubMed

    Gao, Jinsuo; Zhang, Xueying; Xu, Shutao; Liu, Jian; Tan, Feng; Li, Xinyong; Qu, Zhenping; Zhang, Yaobin; Quan, Xie

    2014-03-01

    Pharmaceutical antibiotics, as emerging contaminants, are usually composed of several functional groups that endow them with the ability to interact with adsorbents through different interactions. This makes the preparation of adsorbents tedious and time-consuming to screen appropriate functionalized materials. Herein, we describe the synthesis of clickable SBA-15 and demonstrate its feasibility as a screening material for the adsorption of antibiotics based on similar adsorption trends on materials with similar functional groups obtained by a click reaction and cocondensation/grafting methods.

  9. The Role of Reactive Functional Groups in Adhesive Bonding at the Aramid-Epoxy Interface.

    DTIC Science & Technology

    1986-09-15

    sta end ZIP CeO . 800 North Quincy Street i-q ?AiI 3 Arlington, VA 22217 " ae’Iv o. ’to. 6 -o. !The Role of Reactive Functional . . . 1 12. onsRonfaI...Unclassified SICUMI VY’V Ct.ASSiiICATyO OP ’T-S PAGE I Cont ... 11. The Role of Reactive Functional Groups in Adhesive Bonding at the Aramid-Epoxy...T-1 ROLE OF REACTIVE FUNCTIONAL GROUPS IN ADHESIVI 3ODI;G AT THE ARA fID-EPOXY INTIFA> BY L.S. PENN, T.J. BYERLEY, AND T.K. LIAO 1IDWEST RESEARCR

  10. GPU-based parallel group ICA for functional magnetic resonance data.

    PubMed

    Jing, Yanshan; Zeng, Weiming; Wang, Nizhuan; Ren, Tianlong; Shi, Yingchao; Yin, Jun; Xu, Qi

    2015-04-01

    The goal of our study is to develop a fast parallel implementation of group independent component analysis (ICA) for functional magnetic resonance imaging (fMRI) data using graphics processing units (GPU). Though ICA has become a standard method to identify brain functional connectivity of the fMRI data, it is computationally intensive, especially has a huge cost for the group data analysis. GPU with higher parallel computation power and lower cost are used for general purpose computing, which could contribute to fMRI data analysis significantly. In this study, a parallel group ICA (PGICA) on GPU, mainly consisting of GPU-based PCA using SVD and Infomax-ICA, is presented. In comparison to the serial group ICA, the proposed method demonstrated both significant speedup with 6-11 times and comparable accuracy of functional networks in our experiments. This proposed method is expected to perform the real-time post-processing for fMRI data analysis.

  11. Arrival order among native plant functional groups does not affect invasibility of constructed dune communities.

    PubMed

    Mason, T J; French, K; Jolley, D

    2013-10-01

    Different arrival order scenarios of native functional groups to a site may influence both resource use during development and final community structure. Arrival order may then indirectly influence community resistance to invasion. We present a mesocosm experiment of constructed coastal dune communities that monitored biotic and abiotic responses to different arrival orders of native functional groups. Constructed communities were compared with unplanted mesocosms. We then simulated a single invasion event by bitou (Chrysanthemoides monilifera ssp. rotundata), a dominant exotic shrub of coastal communities. We evaluated the hypothesis that plantings with simultaneous representation of grass, herb and shrub functional groups at the beginning of the experiment would more completely sequester resources and limit invasion than staggered plantings. Staggered plantings in turn would offer greater resource use and invasion resistance than unplanted mesocosms. Contrary to our expectations, there were few effects of arrival order on abiotic variables for the duration of the experiment and arrival order was unimportant in final community invasibility. All planted mesocosms supported significantly more invader germinants and significantly less invader abundance than unplanted mesocosms. Native functional group plantings may have a nurse effect during the invader germination and establishment phase and a competitive function during the invader juvenile and adult phase. Arrival order per se did not affect resource use and community invasibility in our mesocosm experiment. While grass, herb and shrub functional group plantings will not prevent invasion success in restored communities, they may limit final invader biomass.

  12. Identifying organic aerosol sources by comparing functional group composition in chamber and atmospheric particles.

    PubMed

    Russell, Lynn M; Bahadur, Ranjit; Ziemann, Paul J

    2011-03-01

    Measurements of submicron particles by Fourier transform infrared spectroscopy in 14 campaigns in North America, Asia, South America, and Europe were used to identify characteristic organic functional group compositions of fuel combustion, terrestrial vegetation, and ocean bubble bursting sources, each of which often accounts for more than a third of organic mass (OM), and some of which is secondary organic aerosol (SOA) from gas-phase precursors. The majority of the OM consists of alkane, carboxylic acid, hydroxyl, and carbonyl groups. The organic functional groups formed from combustion and vegetation emissions are similar to the secondary products identified in chamber studies. The near absence of carbonyl groups in the observed SOA associated with combustion is consistent with alkane rather than aromatic precursors, and the absence of organonitrate groups can be explained by their hydrolysis in humid ambient conditions. The remote forest observations have ratios of carboxylic acid, organic hydroxyl, and nonacid carbonyl groups similar to those observed for isoprene and monoterpene chamber studies, but in biogenic aerosols transported downwind of urban areas the formation of esters replaces the acid and hydroxyl groups and leaves only nonacid carbonyl groups. The carbonyl groups in SOA associated with vegetation emissions provides striking evidence for the mechanism of esterification as the pathway for possible oligomerization reactions in the atmosphere. Forest fires include biogenic emissions that produce SOA with organic components similar to isoprene and monoterpene chamber studies, also resulting in nonacid carbonyl groups in SOA.

  13. Addition theorem of Slater type orbitals: a numerical evaluation of Barnett Coulson/Löwdin functions

    NASA Astrophysics Data System (ADS)

    Bouferguene, Ahmed

    2005-04-01

    When using the one-centre two-range expansion method to evaluate multicentre integrals over Slater type orbitals (STOs), it may become necessary to compute numerical values of the corresponding Fourier coefficients, also known as Barnett-Coulson/Löwdin Functions (BCLFs) (Bouferguene and Jones 1998 J. Chem. Phys. 109 5718). To carry out this task, it is crucial to not only have a stable numerical procedure but also a fast algorithm. In previous work (Bouferguene and Rinaldi 1994 Int. J. Quantum Chem. 50 21), BCLFs were represented by a double integral which led to a numerically stable algorithm but this turned out to be disappointingly time consuming. The present work aims at exploring another path in which BCLFs are represented either by an infinite series involving modified Bessel functions {\\bf K}_{\

  14. Synergistic effect between defect sites and functional groups on the hydrolysis of cellulose over activated carbon.

    PubMed

    Foo, Guo Shiou; Sievers, Carsten

    2015-02-01

    The chemical oxidation of activated carbon by H2 O2 and H2 SO4 is investigated, structural and chemical modifications are characterized, and the materials are used as catalysts for the hydrolysis of cellulose. Treatment with H2 O2 enlarges the pore size and imparts functional groups such as phenols, lactones, and carboxylic acids. H2 SO4 treatment targets the edges of carbon sheets primarily, and this effect is more pronounced with a higher temperature. Adsorption isotherms demonstrate that the adsorption of oligomers on functionalized carbon is dominated by van der Waals forces. The materials treated chemically are active for the hydrolysis of cellulose despite the relative weakness of most of their acid sites. It is proposed that a synergistic effect between defect sites and functional groups enhances the activity by inducing a conformational change in the glucan chains if they are adsorbed at defect sites. This activates the glycosidic bonds for hydrolysis by in-plane functional groups.

  15. Driving factors of the phytoplankton functional groups in a deep Mediterranean reservoir.

    PubMed

    Becker, Vanessa; Caputo, Luciano; Ordóñez, Jaime; Marcé, Rafael; Armengol, Joan; Crossetti, Luciane O; Huszar, Vera L M

    2010-06-01

    The control of phytoplankton growth is mainly related to the availability of light and nutrients. Both may select phytoplankton species, but only if they occur in limiting amounts. During the last decade, the functional groups approach, based on the physiological, morphological and ecological attributes of the species, has proved to be a more efficient way to analyze seasonal changes in phytoplankton biomass. We analysed the dynamics of the phytoplankton functional groups sensu Reynolds, recognising the driving forces (light, mixing regime, and nutrients) in the Sau Reservoir, based on a one-year cycle (monthly surface-water sampling). The Sau Reservoir is a Mediterranean water-supply reservoir with a canyon-shaped basin and a clear and mixed epilimnion layer. The long stratification period and high light availability led to high phytoplankton biomass (110.8 fresh-weight mg L(-1)) in the epilimnion during summer. The reservoir showed P-limitation for phytoplankton growth in this period. All functional groups included one or more species (X2-Rhodomonas spp.; Y-Cryptomonas spp.; F-Oocystis lacustris; K-Aphanocapsa spp.) selected by resources, especially phosphorus. Species of Cryptomonas (group Y) dominated during the mixing period (winter season) in conditions of low light and relatively high availability of dissolved nutrients. Increases in water-column stability during spring stratification led to phytoplankton biomass increases due to the dominance of small flagellate functional groups (X2 and X3, chrysophyceans). The colonial chlorophycean O. lacustris (group F) peaked during the mid-summer stratification, when the mixed epilimnion was clearly depleted in nutrients, especially SRP. High temperature and increases in nutrient concentration during the end-summer and mid-autumn resulted in a decrease of green algae (group F) and increase of Aphanocapsa spp. (cyanobacteria, group K) and dinoflagellates (group L(o)). The study also revealed the important role of

  16. Longitudinal functional additive model with continuous proportional outcomes for physical activity data.

    PubMed

    Li, Haocheng; Kozey-Keadle, Sarah; Kipnis, Victor; Carroll, Raymond J

    2016-01-01

    Motivated by physical activity data obtained from the BodyMedia FIT device (www.bodymedia.com), we take a functional data approach for longitudinal studies with continuous proportional outcomes. The functional structure depends on three factors. In our three-factor model, the regression structures are specified as curves measured at various factor-points with random effects that have a correlation structure. The random curve for the continuous factor is summarized using a few important principal components. The difficulties in handling the continuous proportion variables are solved by using a quasilikelihood type approximation. We develop an efficient algorithm to fit the model, which involves the selection of the number of principal components. The method is evaluated empirically by a simulation study. This approach is applied to the BodyMedia data with 935 males and 84 consecutive days of observation, for a total of 78, 540 observations. We show that sleep efficiency increases with increasing physical activity, while its variance decreases at the same time.

  17. 46 CFR Appendix F to Subpart C of... - Optional Rider for Additional NVOCC Financial Responsibility for Group Bonds [Optional Rider to...

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 9 2011-10-01 2011-10-01 false Optional Rider for Additional NVOCC Financial Responsibility for Group Bonds F Appendix F to Subpart C of Part 515 Shipping FEDERAL MARITIME COMMISSION... Against Ocean Transportation Intermediaries Pt. 515, Subpt. C, App. F Appendix F to Subpart C of Part...

  18. 46 CFR Appendix F to Subpart C of... - Optional Rider for Additional NVOCC Financial Responsibility for Group Bonds [Optional Rider to...

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... 46 Shipping 9 2010-10-01 2010-10-01 false Optional Rider for Additional NVOCC Financial Responsibility for Group Bonds F Appendix F to Subpart C of Part 515 Shipping FEDERAL MARITIME COMMISSION... Against Ocean Transportation Intermediaries Pt. 515, Subpt. C, App. F Appendix F to Subpart C of Part...

  19. Modeling phytoplankton community in reservoirs. A comparison between taxonomic and functional groups-based models.

    PubMed

    Di Maggio, Jimena; Fernández, Carolina; Parodi, Elisa R; Diaz, M Soledad; Estrada, Vanina

    2016-01-01

    In this paper we address the formulation of two mechanistic water quality models that differ in the way the phytoplankton community is described. We carry out parameter estimation subject to differential-algebraic constraints and validation for each model and comparison between models performance. The first approach aggregates phytoplankton species based on their phylogenetic characteristics (Taxonomic group model) and the second one, on their morpho-functional properties following Reynolds' classification (Functional group model). The latter approach takes into account tolerance and sensitivity to environmental conditions. The constrained parameter estimation problems are formulated within an equation oriented framework, with a maximum likelihood objective function. The study site is Paso de las Piedras Reservoir (Argentina), which supplies water for consumption for 450,000 population. Numerical results show that phytoplankton morpho-functional groups more closely represent each species growth requirements within the group. Each model performance is quantitatively assessed by three diagnostic measures. Parameter estimation results for seasonal dynamics of the phytoplankton community and main biogeochemical variables for a one-year time horizon are presented and compared for both models, showing the functional group model enhanced performance. Finally, we explore increasing nutrient loading scenarios and predict their effect on phytoplankton dynamics throughout a one-year time horizon.

  20. Local and Regional Determinants of an Uncommon Functional Group in Freshwater Lakes and Ponds

    PubMed Central

    McCann, Michael James

    2015-01-01

    A combination of local and regional factors and stochastic forces is expected to determine the occurrence of species and the structure of communities. However, in most cases, our understanding is incomplete, with large amounts of unexplained variation. Using functional groups rather than individual species may help explain the relationship between community composition and conditions. In this study, I used survey data from freshwater lakes and ponds to understand factors that determine the presence of the floating plant functional group in the northeast United States. Of the 176 water bodies surveyed, 104 (59.1%) did not contain any floating plant species. The occurrence of this functional group was largely determined by local abiotic conditions, which were spatially autocorrelated across the region. A model predicting the presence of the floating plant functional group performed similarly to the best species-specific models. Using a permutation test, I also found that the observed prevalence of floating plants is no different than expected by random assembly from a species pool of its size. These results suggest that the size of the species pool interacts with local conditions in determining the presence of a functional group. Nevertheless, a large amount of unexplained variation remains, attributable to either stochastic species occurrence or incomplete predictive models. The simple permutation approach in this study can be extended to test alternative models of community assembly. PMID:26121636

  1. The dual roles of functional groups in the photoluminescence of graphene quantum dots.

    PubMed

    Wang, Shujun; Cole, Ivan S; Zhao, Dongyuan; Li, Qin

    2016-04-14

    The photoluminescent properties of graphene nanoparticle (named graphene quantum dots) have attracted significant research attention in recent years owing to their profound application potential. However, the photoluminescence (PL) origin of this class of nanocarbons is still unclear. In this paper, combining direct experimental evidence enabled by a facile size-tunable oxygenated graphene quantum dots (GQDs) synthesis method and theoretical calculations, the roles of the aromatic core, functional groups and disordered structures (i.e. defects and sp(3) carbon) in the PL of oxygenated GQDs are elucidated in detail. In particular, we found that the functional groups on GQDs play dual roles in the overall emission: (1) they enable π* → n and σ* → n transitions, resulting in a molecular type of PL, spectrally invariable with change of particle size or excitation energy; (2) similar to defects and sp(3) carbon, functional groups also induce structural deformation to the aromatic core, leading to mid-gap states or, in other words, energy traps, causing π* → mid-gap states → π transitions. Therefore, functional groups contribute to both the blue edge and the red shoulder of GQDs' PL spectra. The new insights on the role of functional groups in PL of fluorescent nanocarbons will enable better designs of this new class of materials.

  2. Titanium-Based Hip Stems with Drug Delivery Functionality through Additive Manufacturing.

    PubMed

    Bezuidenhout, Martin B; Dimitrov, Dimitar M; van Staden, Anton D; Oosthuizen, Gert A; Dicks, Leon M T

    2015-01-01

    Postoperative infections are a major concern in patients that receive implants. These infections generally occur in areas with poor blood flow and pathogens do not always respond to antibiotic treatment. With the latest developments in nanotechnology, the incorporation of antibiotics into prosthetic implants may soon become a standard procedure. The success will, however, depend on the ability to control the release of antibiotics at concentrations high enough to prevent the development of antibiotic-resistant strains. Through additive manufacturing, antibiotics can be incorporated into cementless femoral stems to produce prosthetic devices with antimicrobial properties. With the emerging increase in resistance to antibiotics, the incorporation of antimicrobial compounds other than antibiotics, preferably drugs with a broader spectrum of antimicrobial activity, will have to be explored. This review highlights the microorganisms associated with total hip arthroplasty (THA), discusses the advantages and disadvantages of the latest materials used in hip implants, compares different antimicrobial agents that could be incorporated, and addresses novel ideas for future research.

  3. Effects of chemical functional groups on elemental mercury adsorption on carbonaceous surfaces.

    PubMed

    Liu, Jing; Cheney, Marcos A; Wu, Fan; Li, Meng

    2011-02-15

    A systematic theoretical study using density functional theory is performed to provide molecular-level understanding of the effects of chemical functional groups on mercury adsorption on carbonaceous surfaces. The zigzag and armchair edges were used in modeling the carbonaceous surfaces to simulate different adsorption sites. The edge atoms on the upper side of the models are unsaturated to simulate active sites. All calculations (optimizations, energies, and frequencies) were made at B3PW91 density functional theory level, using RCEP60VDZ basis set for mercury and 6-31G(d) pople basis set for other atoms. The results indicate that the embedding of halogen atom can increase the activity of its neighboring site which in turn increases the adsorption capacity of the carbonaceous surface for Hg(0). The adsorption belongs to chemisorptions, which is in good agreement with the experimental results. For the effects of oxygen functional groups, lactone, carbonyl and semiquinone favor Hg(0) adsorption because they increase the neighboring site's activity for mercury adsorption. On the contrary, phenol and carboxyl functional groups show a physisorption of Hg(0), and reduce Hg capture. This result can explain the seemingly conflicting experimental results reported in the literature concerning the influence of oxygen functional groups on mercury adsorption on carbonaceous surface.

  4. Organic-inorganic hybrid foams with diatomite addition: Effect on functional properties

    NASA Astrophysics Data System (ADS)

    Verdolotti, L.; D'Auria, M.; Lavorgna, M.; Vollaro, P.; Iannace, S.; Capasso, I.; Galzerano, B.; Caputo, D.; Liguori, B.

    2016-05-01

    Organic-inorganic hybrid foams were prepared by using metakaolin, diatomite as a partial (or total) replacement of metakaolin, as matrix, silicon and whipped protein as pore forming. The foamed systems were hardened at defined temperature and time and then characterized by mechanical point of view through compression tests and by functional point of view through fire reaction and acoustic tests. The experimental findings highlighted that the replacement of diatomite in the formulation affected the morphological structure of the foams and consequently their mechanical properties. In particular, the consolidation mechanism in the diatomite based-hybrid foams changed from geopolymerization to a silicate polycondensation mechanism. Therefore, mechanical performances enhanced with increasing of the diatomite content. Fire reaction tests, such as non-combustibility and cone calorimeter tests, showed positive thermal inertia of samples regardless of the content of diatomite.

  5. Synthesis of highly functionalized chiral 3,3'-disubstituted oxindoles via an organocatalytic enantioselective Michael addition of nitroalkanes to indolylidenecyanoacetates.

    PubMed

    Liu, Lu; Wu, Deyan; Zheng, Shu; Li, Tengfei; Li, Xiangmin; Wang, Sinan; Li, Jian; Li, Hao; Wang, Wei

    2012-01-06

    An efficient bifunctional cinchona alkaloid derived thiourea-promoted enantioselective conjugate addition of nitroalkanes to indolylidenecyanoacetates has been developed under neat conditions. The process leads to synthetically interesting densely functionalized 3,3'-disubstituted oxindoles with creation of up to three stereogenic centers.

  6. Catalytic asymmetric tandem Friedel-Crafts alkylation/Michael addition reaction for the synthesis of highly functionalized chromans.

    PubMed

    Peng, Jiahuan; Du, Da-Ming

    2013-01-01

    The enantioselective tandem Friedel-Crafts alkylation/Michael addition reaction of indoles with nitroolefin enoates catalyzed by a diphenylamine-linked bis(oxazoline)-Zn(OTf)2 complex was investigated. This tandem reaction afforded functionalized chiral chromans in good yields with moderate to high stereoselectivities (up to 95:5 dr, up to 99% ee).

  7. Titanium-Based Hip Stems with Drug Delivery Functionality through Additive Manufacturing

    PubMed Central

    Bezuidenhout, Martin B.; Dimitrov, Dimitar M.; van Staden, Anton D.; Oosthuizen, Gert A.; Dicks, Leon M. T.

    2015-01-01

    Postoperative infections are a major concern in patients that receive implants. These infections generally occur in areas with poor blood flow and pathogens do not always respond to antibiotic treatment. With the latest developments in nanotechnology, the incorporation of antibiotics into prosthetic implants may soon become a standard procedure. The success will, however, depend on the ability to control the release of antibiotics at concentrations high enough to prevent the development of antibiotic-resistant strains. Through additive manufacturing, antibiotics can be incorporated into cementless femoral stems to produce prosthetic devices with antimicrobial properties. With the emerging increase in resistance to antibiotics, the incorporation of antimicrobial compounds other than antibiotics, preferably drugs with a broader spectrum of antimicrobial activity, will have to be explored. This review highlights the microorganisms associated with total hip arthroplasty (THA), discusses the advantages and disadvantages of the latest materials used in hip implants, compares different antimicrobial agents that could be incorporated, and addresses novel ideas for future research. PMID:26504776

  8. Improvement of attenuation functions of a clayey sandstone for landfill leachate containment by bentonite addition.

    PubMed

    Ruiz, Ana I; Fernández, Raúl; Sánchez Jiménez, Nicanor; Rodríguez Rastrero, Manuel; Regadío, Mercedes; de Soto, Isabel S; Cuevas, Jaime

    2012-03-01

    Enhanced sand-clay mixtures have been prepared by using a sandstone arkosic material and have been evaluated for consideration as landfill liners. A lab-scale test was carried out under controlled conditions with different amended natural sandstones whereby leachate was passed through the compacted mixtures. The compacted samples consisted of siliceous sand (quartz-feldspar sand separated from the arkose sandstone) and clay (purified clay from arkose sandstone and two commercial bentonites) materials that were mixed in different proportions. The separation of mineral materials from a common and abundant natural source, for soil protection purposes, is proposed as an economic and environmentally efficient practice. The liner qualities were compared for their mineralogical, physicochemical and major ions transport and adsorption properties. Although all samples fulfilled hydraulic conductivity requirements, the addition of bentonite to arkose sandstone was determined to be an effective strategy to decrease the permeability of the soil and to improve the pollutants retention. The clay materials from arkose sandstone also contributed to pollutant retention by a significant improvement of the cation exchange capacity of the bulk material. However, the mixtures prepared with clay materials from the arkose, exhibited a slight increase of hydraulic conductivity. This effect has to be further evaluated.

  9. Is the structural diversity of tripeptides sufficient for developing functional food additives with satisfactory multiple bioactivities?

    NASA Astrophysics Data System (ADS)

    Wang, Jian-Hui; Liu, Yong-Le; Ning, Jing-Heng; Yu, Jian; Li, Xiang-Hong; Wang, Fa-Xiang

    2013-05-01

    Multifunctional peptides have attracted increasing attention in the food science community because of their therapeutic potential, low toxicity and rapid intestinal absorption. However, previous study demonstrated that the limited structural variations make it difficult to optimize dipeptide molecules in a good balance between desirable and undesirable properties (F. Tian, P. Zhou, F. Lv, R. Song, Z. Li, J. Pept. Sci. 13 (2007) 549-566). In the present work, we attempt to answer whether the structural diversity is sufficient for a tripeptide to have satisfactory multiple bioactivities. Statistical test, structural examination and energetic analysis confirm that peptides of three amino acids long can bind tightly to human angiotensin converting enzyme (ACE) and thus exert significant antihypertensive efficacy. Further quantitative structure-activity relationship (QSAR) modeling and prediction of all 8000 possible tripeptides reveal that their ACE-inhibitory potency exhibits a good (positive) relationship to antioxidative activity, but has only a quite modest correlation with bitterness. This means that it is possible to find certain tripeptide entities possessing the optimal combination of strong ACE-inhibitory potency, high antioxidative activity and weak bitter taste, which are the promising candidates for developing multifunctional food additives with satisfactory multiple bioactivities. The marked difference between dipeptide and tripeptide can be attributed to the fact that the structural diversity of peptides increases dramatically with a slight change in sequence length.

  10. Glass transition of polystyrene (PS) studied by Raman spectroscopic investigation of its phenyl functional groups

    NASA Astrophysics Data System (ADS)

    Bertoldo Menezes, D.; Reyer, A.; Marletta, A.; Musso, M.

    2017-01-01

    In polymeric materials the glass transition (GT) is a well-known and very important relaxation process related to movements of functional groups in the polymeric chain. In this work, we show the potential of Raman spectroscopy for exploring the GT process in the polymer polystyrene. We collected Raman spectra during a step-by-step heating process of the sample, which allowed us to collect signatures of the GT process from peak parameters of specific vibrational modes, and to verify the GT temperature. Results of the latter were in accordance with published values obtained via other methods. We identified the aromatic ring vibrational modes of the phenyl functional groups to be those which, due to steric hindrance, suffer the largest influence during the GT process. This confirms that Raman spectroscopy can be used as a complementary technique to perform GT investigations in polymeric materials due to its sensitivity to small intermolecular changes affecting vibrational properties of relevant functional side groups.

  11. A new strategy for integrating abundant oxygen functional groups into carbon felt electrode for vanadium redox flow batteries

    PubMed Central

    Kim, Ki Jae; Lee, Seung-Wook; Yim, Taeeun; Kim, Jae-Geun; Choi, Jang Wook; Kim, Jung Ho; Park, Min-Sik; Kim, Young-Jun

    2014-01-01

    The effects of surface treatment combining corona discharge and hydrogen peroxide (H2O2) on the electrochemical performance of carbon felt electrodes for vanadium redox flow batteries (VRFBs) have been thoroughly investigated. A high concentration of oxygen functional groups has been successfully introduced onto the surface of the carbon felt electrodes by a specially designed surface treatment, which is mainly responsible for improving the energy efficiency of VRFBs. In addition, the wettability of the carbon felt electrodes also can be significantly improved. The energy efficiency of the VRFB cell employing the surface modified carbon felt electrodes is improved by 7% at high current density (148 mA cm−2). Such improvement is attributed to the faster charge transfer and better wettability allowed by surface-active oxygen functional groups. Moreover, this method is much more competitive than other surface treatments in terms of processing time, production costs, and electrochemical performance. PMID:25366060

  12. Wigner functions for noncommutative quantum mechanics: A group representation based construction

    NASA Astrophysics Data System (ADS)

    Chowdhury, S. Hasibul Hassan; Ali, S. Twareque

    2015-12-01

    This paper is devoted to the construction and analysis of the Wigner functions for noncommutative quantum mechanics, their marginal distributions, and star-products, following a technique developed earlier, viz, using the unitary irreducible representations of the group GNC, which is the three fold central extension of the Abelian group of ℝ4. These representations have been exhaustively studied in earlier papers. The group GNC is identified with the kinematical symmetry group of noncommutative quantum mechanics of a system with two degrees of freedom. The Wigner functions studied here reflect different levels of non-commutativity—both the operators of position and those of momentum not commuting, the position operators not commuting and finally, the case of standard quantum mechanics, obeying the canonical commutation relations only.

  13. Wigner functions for noncommutative quantum mechanics: A group representation based construction

    SciTech Connect

    Chowdhury, S. Hasibul Hassan; Ali, S. Twareque

    2015-12-15

    This paper is devoted to the construction and analysis of the Wigner functions for noncommutative quantum mechanics, their marginal distributions, and star-products, following a technique developed earlier, viz, using the unitary irreducible representations of the group G{sub NC}, which is the three fold central extension of the Abelian group of ℝ{sup 4}. These representations have been exhaustively studied in earlier papers. The group G{sub NC} is identified with the kinematical symmetry group of noncommutative quantum mechanics of a system with two degrees of freedom. The Wigner functions studied here reflect different levels of non-commutativity—both the operators of position and those of momentum not commuting, the position operators not commuting and finally, the case of standard quantum mechanics, obeying the canonical commutation relations only.

  14. Effects of Germinated Brown Rice Addition on the Flavor and Functionality of Yogurt.

    PubMed

    Kim, Mi-Hye; Ahn, Sung-Il; Lim, Chan-Mook; Jhoo, Jin-Woo; Kim, Gur-Yoo

    2016-01-01

    This study aimed to investigate the functional and physicochemical properties of yogurt, supplemented with germinated brown rice (GBR) containing γ-aminobutyric acid (GABA), during storage. GBR was produced by soaking brown rice at 30℃, and saccharified germinated brown rice (SGBR) was produced by treating brown rice with α- and β-amylase for 1 h, at 80℃ and 60℃, respectively. Yogurt was manufactured using a commercial starter (YC-X11, CHR. Hansen, Denmark) at 37℃ for 12 h. The fatty acids and GABA contents were analyzed using GC and HPLC, respectively. The fatty acids in the cereal samples consisted of oleic, linoleic, and palmitic acid. The portion of oleic acid was the highest, at 35.65% in GBR, and 32.16% in SGBR. During germination, the oleic acid content increased, whereas linolenic and palmitic acid contents from GBR tended to decrease. Although the portion of saturated fatty acids, such as stearic and myristic acid, decreased significantly (p<0.05), that of unsaturated fatty acids, such as oleic and linoleic acid, increased with an increase in supplementation of BR, GBR, or SGBR in the yogurt. The yogurt, supplemented with cereal samples, showed a tendency of an increase in the concentration of GABA with an increase in the supplementation of the cereal samples. However, yogurt supplemented with GBR showed the highest concentration of GABA, regardless of the supplementation of the cereal samples. These results indicated that yogurt supplemented with BR, GBR, or SGBR could be a promising dairy product.

  15. Functional grouping and cortical–subcortical interactions in emotion: A meta-analysis of neuroimaging studies

    PubMed Central

    Kober, Hedy; Barrett, Lisa Feldman; Joseph, Josh; Bliss-Moreau, Eliza; Lindquist, Kristen; Wager, Tor D.

    2009-01-01

    We performed an updated quantitative meta-analysis of 162 neuroimaging studies of emotion using a novel multi-level kernel-based approach, focusing on locating brain regions consistently activated in emotional tasks and their functional organization into distributed functional groups, independent of semantically defined emotion category labels (e.g., “anger,” “fear”). Such brain-based analyses are critical if our ways of labeling emotions are to be evaluated and revised based on consistency with brain data. Consistent activations were limited to specific cortical sub-regions, including multiple functional areas within medial, orbital, and inferior lateral frontal cortices. Consistent with a wealth of animal literature, multiple subcortical activations were identified, including amygdala, ventral striatum, thalamus, hypothalamus, and periaqueductal gray. We used multivariate parcellation and clustering techniques to identify groups of co-activated brain regions across studies. These analyses identified six distributed functional groups, including medial and lateral frontal groups, two posterior cortical groups, and paralimbic and core limbic/brainstem groups. These functional groups provide information on potential organization of brain regions into large-scale networks. Specific follow-up analyses focused on amygdala, periaqueductal gray (PAG), and hypothalamic (Hy) activations, and identified frontal cortical areas co-activated with these core limbic structures. While multiple areas of frontal cortex co-activated with amygdala sub-regions, a specific region of dorsomedial prefrontal cortex (dmPFC, Brodmann’s Area 9/32) was the only area co-activated with both PAG and Hy. Subsequent mediation analyses were consistent with a pathway from dmPFC through PAG to Hy. These results suggest that medial frontal areas are more closely associated with core limbic activation than their lateral counterparts, and that dmPFC may play a particularly important role in the

  16. Hydrological-niche models predict water plant functional group distributions in diverse wetland types.

    PubMed

    Deane, David C; Nicol, Jason M; Gehrig, Susan L; Harding, Claire; Aldridge, Kane T; Goodman, Abigail M; Brookes, Justin D

    2017-03-06

    Human use of water resources threatens environmental water supplies. If resource managers are to develop policies that avoid unacceptable ecological impacts, some means to predict ecosystem response to changes in water availability is necessary. This is difficult to achieve at spatial-scales relevant for water resource management because of the high natural variability in ecosystem hydrology and ecology. Water plant functional groups classify species with similar hydrological niche preferences together, allowing a qualitative means to generalise community responses to changes in hydrology. We tested the potential for functional groups in making quantitative prediction of water-plant-functional-group distributions across diverse wetland types over a large geographical extent. We sampled wetlands covering a broad range of hydrogeomorphic and salinity conditions in South Australia, collecting both hydrological and floristic data from 697 quadrats across 28 wetland hydrological gradients. We built hydrological-niche models for eight water plant functional groups using a range of candidate models combining different surface inundation metrics. We then tested the predictive performance of top-ranked individual and averaged models for each functional group. Cross validation showed models achieved acceptable predictive performance, with correct classification rates in the range 0.68 - 0.95. Model predictions can be made at any spatial scale that hydrological data are available and could be implemented in a geographical information system. We show the response of water plant functional groups to inundation is consistent enough across diverse wetland types to quantify the probability of hydrological impacts over regional spatial scales. This article is protected by copyright. All rights reserved.

  17. Protection and deprotection approach for the introduction of functional groups into metal-organic frameworks.

    PubMed

    Yamada, Teppei; Kitagawa, Hiroshi

    2009-05-13

    A noncoordinating hydroxyl group was introduced into a metal-organic framework (MOF) by a procedure involving a protection, complexation, and deprotection (PCD) reaction sequence, and the crystal structure of a novel MOF, [Zn(dhybdc)(bpy)] x 4 DMF (1), was determined. 1 did not have an interpenetrated structure. The three-dimensional pores had large apertures. Results showed that the PCD method is a novel synthetic method for the introduction of various functional groups into MOFs.

  18. Testing Group Differences in Brain Functional Connectivity: Using Correlations or Partial Correlations?

    PubMed Central

    Kim, Junghi; Wozniak, Jeffrey R.; Mueller, Bryon A.

    2015-01-01

    Abstract Resting-state functional magnetic resonance imaging allows one to study brain functional connectivity, partly motivated by evidence that patients with complex disorders, such as Alzheimer's disease, may have altered functional brain connectivity patterns as compared with healthy subjects. A functional connectivity network describes statistical associations of the neural activities among distinct and distant brain regions. Recently, there is a major interest in group-level functional network analysis; however, there is a relative lack of studies on statistical inference, such as significance testing for group comparisons. In particular, it is still debatable which statistic should be used to measure pairwise associations as the connectivity weights. Many functional connectivity studies have used either (full or marginal) correlations or partial correlations for pairwise associations. This article investigates the performance of using either correlations or partial correlations for testing group differences in brain connectivity, and how sparsity levels and topological structures of the connectivity would influence statistical power to detect group differences. Our results suggest that, in general, testing group differences in networks deviates from estimating networks. For example, high regularization in both covariance matrices and precision matrices may lead to higher statistical power; in particular, optimally selected regularization (e.g., by cross-validation or even at the true sparsity level) on the precision matrices with small estimation errors may have low power. Most importantly, and perhaps surprisingly, using either correlations or partial correlations may give very different testing results, depending on which of the covariance matrices and the precision matrices are sparse. Specifically, if the precision matrices are sparse, presumably and arguably a reasonable assumption, then using correlations often yields much higher powered and more

  19. Water Contact Angle Dependence with Hydroxyl Functional Groups on Silica Surfaces under CO2 Sequestration Conditions.

    PubMed

    Chen, Cong; Zhang, Ning; Li, Weizhong; Song, Yongchen

    2015-12-15

    Functional groups on silica surfaces under CO2 sequestration conditions are complex due to reactions among supercritical CO2, brine and silica. Molecular dynamics simulations have been performed to investigate the effects of hydroxyl functional groups on wettability. It has been found that wettability shows a strong dependence on functional groups on silica surfaces: silanol number density, space distribution, and deprotonation/protonation degree. For neutral silica surfaces with crystalline structure (Q(3), Q(3)/Q(4), Q(4)), as silanol number density decreases, contact angle increases from 33.5° to 146.7° at 10.5 MPa and 318 K. When Q(3) surface changes to an amorphous structure, water contact angle increases 20°. Water contact angle decreases about 12° when 9% of silanol groups on Q(3) surface are deprotonated. When the deprotonation degree increases to 50%, water contact angle decreases to 0. The dependence of wettability on silica surface functional groups was used to analyze contact angle measurement ambiguity in literature. The composition of silica surfaces is complicated under CO2 sequestration conditions, the results found in this study may help to better understand wettability of CO2/brine/silica system.

  20. A novel joint sparse partial correlation method for estimating group functional networks.

    PubMed

    Liang, Xiaoyun; Connelly, Alan; Calamante, Fernando

    2016-03-01

    Advances in graph theory have provided a powerful tool to characterize brain networks. In particular, functional networks at group-level have great appeal to gain further insight into complex brain function, and to assess changes across disease conditions. These group networks, however, often have two main limitations. First, they are popularly estimated by directly averaging individual networks that are compromised by confounding variations. Secondly, functional networks have been estimated mainly through Pearson cross-correlation, without taking into account the influence of other regions. In this study, we propose a sparse group partial correlation method for robust estimation of functional networks based on a joint graphical models approach. To circumvent the issue of choosing the optimal regularization parameters, a stability selection method is employed to extract networks. The proposed method is, therefore, denoted as JGMSS. By applying JGMSS across simulated datasets, the resulting networks show consistently higher accuracy and sensitivity than those estimated using an alternative approach (the elastic-net regularization with stability selection, ENSS). The robustness of the JGMSS is evidenced by the independence of the estimated networks to choices of the initial set of regularization parameters. The performance of JGMSS in estimating group networks is further demonstrated with in vivo fMRI data (ASL and BOLD), which show that JGMSS can more robustly estimate brain hub regions at group-level and can better control intersubject variability than it is achieved using ENSS.

  1. First-Principles Density Functional Theory Modeling Study on the Redox Chemistry of Graphene Oxides Affected by Placement Geometry of Oxygen Functional Groups

    NASA Astrophysics Data System (ADS)

    Kim, Sunghee; Kim, Ki Chul; Lee, Seung Woo; Jang, Seung Soon

    2015-03-01

    To date, lithium-ion batteries have been extensively gained attention due to their promising potential in the industry. Despite their promising properties, improving their poor power density is still needed for practical applications. In addition, sustaining the high redox potential in the lithium-ion batteries is prerequisite for exhibiting the high energy and power densities. Recently, layered carbon materials including graphenes and carbon nanotubes have been paid special attention as promising electrode candidates with high power densities due to their exceptionally high surface area and active oxygen functional groups on their surfaces. However, the lack of reliable information on the redox chemistry of the candidates is the obstacle to be uncovered for practical applications. In this study, we investigated the redox chemistry of graphene oxides cluster models with well-controlled hydroxyl functional groups at the edge. First-principles density functional theory approach was employed to understand the geometric effect of the incorporated hydroxyl functional groups on the redox chemistry. Our study will provide an insight on the strategy for improving the redox potentials of graphene-based electrode candidates.

  2. Fluorescent macrocyclic probes with pendant functional groups as markers of acidic organelles within live cells.

    PubMed

    Wadhavane, Prashant D; Izquierdo, M Ángeles; Lutters, Dennis; Burguete, M Isabel; Marín, María J; Russell, David A; Galindo, Francisco; Luis, Santiago V

    2014-02-07

    A new family of acidity sensitive fluorescent macrocycles has been synthesized and fully characterized. Their photophysical properties including emission quantum yield and fluorescence lifetime have been determined. The acid-base properties of the new molecules can be tuned by the incorporation of pendant functional groups. The nature of such functional groups (carboxylic acid or ester) influences dramatically the pKa of the probes, two compounds of which exhibit low values. Preliminary intracellular studies using confocal microscopy together with emission spectra of the probes from the cellular environment have shown that the synthesized fluorescent macrocycles mark the acidic organelles of RAW 264.7 macrophage cells.

  3. Group I Metabotropic Glutamate Receptor Interacting Proteins: Fine-Tuning Receptor Functions in Health and Disease

    PubMed Central

    Kalinowska, Magdalena; Francesconi, Anna

    2016-01-01

    Group I metabotropic glutamate receptors mediate slow excitatory neurotransmission in the central nervous system and are critical to activity-dependent synaptic plasticity, a cellular substrate of learning and memory. Dysregulated receptor signaling is implicated in neuropsychiatric conditions ranging from neurodevelopmental to neurodegenerative disorders. Importantly, group I metabotropic glutamate receptor signaling functions can be modulated by interacting proteins that mediate receptor trafficking, expression and coupling efficiency to signaling effectors. These interactions afford cell- or pathway-specific modulation to fine-tune receptor function, thus representing a potential target for pharmacological interventions in pathological conditions. PMID:27296642

  4. Effects of Germinated Brown Rice Addition on the Flavor and Functionality of Yogurt

    PubMed Central

    2016-01-01

    This study aimed to investigate the functional and physicochemical properties of yogurt, supplemented with germinated brown rice (GBR) containing γ-aminobutyric acid (GABA), during storage. GBR was produced by soaking brown rice at 30℃, and saccharified germinated brown rice (SGBR) was produced by treating brown rice with α- and β-amylase for 1 h, at 80℃ and 60℃, respectively. Yogurt was manufactured using a commercial starter (YC-X11, CHR. Hansen, Denmark) at 37℃ for 12 h. The fatty acids and GABA contents were analyzed using GC and HPLC, respectively. The fatty acids in the cereal samples consisted of oleic, linoleic, and palmitic acid. The portion of oleic acid was the highest, at 35.65% in GBR, and 32.16% in SGBR. During germination, the oleic acid content increased, whereas linolenic and palmitic acid contents from GBR tended to decrease. Although the portion of saturated fatty acids, such as stearic and myristic acid, decreased significantly (p<0.05), that of unsaturated fatty acids, such as oleic and linoleic acid, increased with an increase in supplementation of BR, GBR, or SGBR in the yogurt. The yogurt, supplemented with cereal samples, showed a tendency of an increase in the concentration of GABA with an increase in the supplementation of the cereal samples. However, yogurt supplemented with GBR showed the highest concentration of GABA, regardless of the supplementation of the cereal samples. These results indicated that yogurt supplemented with BR, GBR, or SGBR could be a promising dairy product. PMID:27621692

  5. [Responses of ground arthropod functional groups to the enclosure of grazing grassland in desert steppe].

    PubMed

    Liu, Ren-tao; Li, Xue-bin; Xin, Ming; Ma, Lin; Liu, Kai

    2011-08-01

    With the support of the National Resources Monitoring Station in Yanchi County of Ningxia, an investigation was conducted on the ground arthropods, vegetations, and soil properties in the enclosed and un-enclosed grazing grassland in desert steppe. In the meantime, the functional groups of ground arthropods were classified according to their feeding habits. The ground arthropods in the desert steppe could be classified into four functional groups, i.e., predatory, phytophagous, saprophagous, and omnivorous, among which, predatory and phytophagous groups were dominant in quantity, and phytophagous and saprophagous groups were predominant in biomass, implying that the ground arthropod in desert steppe was mainly characterized by phytophagous arthropods. Enclosure increased the individual and group number of predatory, phytophagous, and omnivorous arthropods as well as the biomass of predatory and omnivorous arthropods, and enhanced the biodiversity of predatory and phytophagous arthropods, which was closely correlated with the vegetation recovery and soil environment improvement, and demonstrated that the enclosure of grazing grassland increased the diversity and complexity of ground arthropod functional groups in desert steppe. Nevertheless, the individual number and biomass of saprophagous arthropods decreased after the enclosure, reflecting the dependence of these arthropods on grazing grassland.

  6. Establishment of a series of alien monosomic addition lines of Japanese bunching onion (Allium fistulosum L.) with extra chromosomes from shallot (A. cepa L. aggregatum group).

    PubMed

    Shigyo, M; Tashiro, Y; Isshiki, S; Miyazaki, S

    1996-12-01

    Forty one plants of alien monosomic addition lines of Allium fistulosum L. with extra chromosomes from A. cepa L. Aggregatum group (FF + nA) were produced through the second backcross of amphidiploids between these two species to A. fistulosum. Identification of the extra chromosomes in the 16 plants by elaborate karyotype analyses indicate that a complete series (eight different types) of the alien monosomic addition lines was established in Allium for the first time in this study. Chromosomal locations of malate dehydrogenase (MDH) gene, triosephosphate isomerase (TPI) gene and 5S rDNA of A. cepa Aggregatum group were determined using the series; The gene locus Mdh-1 was located on 4A, Tpi-1 on 3A and a 5S rDNA locus on 7A. Our previous and present studies using the alien monosomic addition lines revealed 11 genetic markers (isozyme and 5S rDNA) assigned to all eight chromosomes of A. cepa Aggregatum group, and these markers reconfirmed the completion of the series. Extra chromosomes of 25 other plants were examined by means of simple analyses of the chromosome markers and karyotypes. Of the total 41 plants, frequencies of the alien monosomic addition lines with extra chromosomes 1A to 8A were as follows: 1A, 5 plants; 2A, 3; 3A, 5; 4A, 9; 5A, 4; 6A, 2; 7A, 11; and 8A, 2.

  7. Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

    PubMed Central

    Gillett-Kunnath, Miriam M.; Sevov, Slavi C.

    2012-01-01

    Although the first studies of Zintl ions date between the late 1890's and early 1930's they were not structurally characterized until many years later.1,2 Their redox chemistry is even younger, just about ten years old, but despite this short history these deltahedral clusters ions E9n- (E = Si, Ge, Sn, Pb; n = 2, 3, 4) have already shown interesting and diverse reactivity and have been at the forefront of rapidly developing and exciting new chemistry.3-6 Notable milestones are the oxidative coupling of Ge94- clusters to oligomers and infinite chains,7-19 their metallation,14-16,20-25 capping by transition-metal organometallic fragments,26-34 insertion of a transition-metal atom at the center of the cluster which is sometimes combined with capping and oligomerization,35-47 addition of main-group organometallic fragments as exo-bonded substituents,48-50 and functionalization with various organic residues by reactions with organic halides and alkynes.51-58 This latter development of attaching organic fragments directly to the clusters has opened up a new field, namely organo-Zintl chemistry, that is potentially fertile for further synthetic explorations, and it is the step-by-step procedure for the synthesis of germanium-divinyl clusters described herein. The initial steps outline the synthesis of an intermetallic precursor of K4Ge9 from which the Ge94- clusters are extracted later in solution. This involves fused-silica glass blowing, arc-welding of niobium containers, and handling of highly air-sensitive materials in a glove box. The air-sensitive K4Ge9 is then dissolved in ethylenediamine in the box and then alkenylated by a reaction with Me3SiC≡CSiMe3. The reaction is followed by electrospray mass spectrometry while the resulting solution is used for obtaining single crystals containing the functionalized clusters [H2C=CH-Ge9-CH=CH2]2-. For this purpose the solution is centrifuged, filtered, and carefully layered with a toluene solution of 18-crown-6. Left

  8. Synthesis of nine-atom deltahedral Zintl ions of germanium and their functionalization with organic groups.

    PubMed

    Gillett-Kunnath, Miriam M; Sevov, Slavi C

    2012-02-11

    Although the first studies of Zintl ions date between the late 1890's and early 1930's they were not structurally characterized until many years later. Their redox chemistry is even younger, just about ten years old, but despite this short history these deltahedral clusters ions E9(n-) (E = Si, Ge, Sn, Pb; n = 2, 3, 4) have already shown interesting and diverse reactivity and have been at the forefront of rapidly developing and exciting new chemistry. Notable milestones are the oxidative coupling of Ge9(4-) clusters to oligomers and infinite chains, their metallation, capping by transition-metal organometallic fragments, insertion of a transition-metal atom at the center of the cluster which is sometimes combined with capping and oligomerization, addition of main-group organometallic fragments as exo-bonded substituents, and functionalization with various organic residues by reactions with organic halides and alkynes. This latter development of attaching organic fragments directly to the clusters has opened up a new field, namely organo-Zintl chemistry, that is potentially fertile for further synthetic explorations, and it is the step-by-step procedure for the synthesis of germanium-divinyl clusters described herein. The initial steps outline the synthesis of an intermetallic precursor of K4Ge9 from which the Ge9(4-) clusters are extracted later in solution. This involves fused-silica glass blowing, arc-welding of niobium containers, and handling of highly air-sensitive materials in a glove box. The air-sensitive K4Ge9 is then dissolved in ethylenediamine in the box and then alkenylated by a reaction with Me3SiC≡CSiMe3. The reaction is followed by electrospray mass spectrometry while the resulting solution is used for obtaining single crystals containing the functionalized clusters [H2C=CH-Ge9-CH=CH2](2-). For this purpose the solution is centrifuged, filtered, and carefully layered with a toluene solution of 18-crown-6. Left undisturbed for a few days, the so

  9. Chemoselective Reduction and Alkylation of Carbonyl Functions Using Phosphonium Salts as an in Situ Protecting Groups.

    PubMed

    Ohta, Reiya; Fujioka, Hiromichi

    2017-01-01

    Recent progress in the chemoselective reduction and alkylation of carbonyl functions using our in situ protection method is described. Methods that enable reversal or control of the reactivity of a carbonyl functional group are potentially useful. They open up new areas of synthetic organic chemistry and change the concept of retrosynthesis because they remove the need for complicated protection/deprotection sequences. In this account, we discuss the strategy and applications of our in situ protection method using phosphonium salts.

  10. A versatile route to polythiophenes with functional pendant groups using alkyne chemistry

    PubMed Central

    Yang, Li; Emanuelsson, Rikard; Bergquist, Jonas; Strømme, Maria; Sjödin, Martin

    2016-01-01

    A new versatile polythiophene building block, 3-(3,4-ethylenedioxythiophene)prop-1-yne (pyEDOT) (3), is prepared from glycidol in four steps in 28% overall yield. pyEDOT features an ethynyl group on its ethylenedioxy bridge, allowing further functionalization by alkyne chemistry. Its usefulness is demonstrated by a series of functionalized polythiophene derivatives that were obtained by pre- and post-electropolymerization transformations, provided by the synthetic ease of the Sonogashira coupling and click chemistry. PMID:28144339

  11. Modeling Differential Item Functioning Using a Generalization of the Multiple-Group Bifactor Model

    ERIC Educational Resources Information Center

    Jeon, Minjeong; Rijmen, Frank; Rabe-Hesketh, Sophia

    2013-01-01

    The authors present a generalization of the multiple-group bifactor model that extends the classical bifactor model for categorical outcomes by relaxing the typical assumption of independence of the specific dimensions. In addition to the means and variances of all dimensions, the correlations among the specific dimensions are allowed to differ…

  12. Multiconfiguration pair-density functional theory: barrier heights and main group and transition metal energetics.

    PubMed

    Carlson, Rebecca K; Li Manni, Giovanni; Sonnenberger, Andrew L; Truhlar, Donald G; Gagliardi, Laura

    2015-01-13

    Kohn-Sham density functional theory, resting on the representation of the electronic density and kinetic energy by a single Slater determinant, has revolutionized chemistry, but for open-shell systems, the Kohn-Sham Slater determinant has the wrong symmetry properties as compared to an accurate wave function. We have recently proposed a theory, called multiconfiguration pair-density functional theory (MC-PDFT), in which the electronic kinetic energy and classical Coulomb energy are calculated from a multiconfiguration wave function with the correct symmetry properties, and the rest of the energy is calculated from a density functional, called the on-top density functional, that depends on the density and the on-top pair density calculated from this wave function. We also proposed a simple way to approximate the on-top density functional by translation of Kohn-Sham exchange-correlation functionals. The method is much less expensive than other post-SCF methods for calculating the dynamical correlation energy starting with a multiconfiguration self-consistent-field wave function as the reference wave function, and initial tests of the theory were quite encouraging. Here, we provide a broader test of the theory by applying it to bond energies of main-group molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy. Averaged over 56 data points, the mean unsigned error is 3.2 kcal/mol for MC-PDFT, as compared to 6.9 kcal/mol for Kohn-Sham theory with a comparable density functional. MC-PDFT is more accurate on average than complete active space second-order perturbation theory (CASPT2) for main-group small-molecule bond energies, alkyl bond dissociation energies, transition-metal-ligand bond energies, proton affinities, and the water dimerization energy.

  13. Thermochemical Properties and Bond Dissociation Energies for Fluorinated Methanol, CH3-xFxOH, and Fluorinated Methyl Hydroperoxides, CH3-xFxOOH: Group Additivity.

    PubMed

    Wang, Heng; Bozzelli, Joseph W

    2016-09-08

    Oxygenated fluorocarbons are routinely found in sampling of environmental soils and waters as a result of the widespread use of fluoro and chlorofluoro carbons as heat transfer fluids, inert materials, polymers, fire retardants and solvents; the influence of these chemicals on the environment is a growing concern. The thermochemical properties of these species are needed for understanding their stability and reactions in the environment and in thermal process. Structures and thermochemical properties on the mono- to trifluoromethanol, CH3-xFxOH, and fluoromethyl hydroperoxide, CH3-xFxOOH (1 ≤ x ≤ 3), are determined by CBS-QB3, CBS-APNO, and G4 calculations. Entropy, S°298, and heat capacities, Cp(T)'s (300 ≤ T/K ≤ 1500) from vibration, translation, and external rotation contributions are calculated on the basis of the vibration frequencies and structures obtained from the B3LYP/6-31+G(d,p) density functional method. Potential barriers for the internal rotations are also calculated from this method and used to calculate hindered rotor contributions to S°298 and Cp(T)'s using direct integration over energy levels of the internal rotational potentials. Standard enthalpies of formation, ΔfH°298 (units in kcal mol(-1)) are CH2FOOH (-83.7), CHF2OOH (-138.1), CF3OOH (-193.6), CH2FOO(•) (-44.9), CHF2OO(•) (-99.6), CF3OO(•) (-153.8), CH2FOH (-101.9), CHF2OH (-161.6), CF3OH (-218.1), CH2FO(•) (-49.1), CHF2O(•) (-97.8), CF3O(•) (-150.5), CH2F(•) (-7.6), CHF2(•) (-58.8), and CF3(•) (-112.6). Bond dissociation energies for the R-OOH, RO-OH, ROO-H, R-OO(•), RO-O(•), R-OH, RO-H, R-O(•), and R-H bonds are determined and compared with methyl hydroperoxide to observe the trends from added fluoro substitutions. Enthalpy of formation for the fluoro-hydrocarbon oxygen groups C/F/H2/O, C/F2/H/O, C/F3/O, are derived from the above fluorinated methanol and fluorinated hydroperoxide species for use in Benson's Group Additivity. It was determined that

  14. Asymmetric Catalytic Enantio- and Diastereoselective Boron Conjugate Addition Reactions of α-Functionalized α,β-Unsaturated Carbonyl Substrates.

    PubMed

    Xie, Jian-Bo; Lin, Siqi; Qiao, Shuo; Li, Guigen

    2016-08-05

    An efficient catalytic system has been established for the asymmetric boron conjugate addition of B2pin2 onto α-functionalized (involving C, N, O, and Cl) α,β-unsaturated carbonyls under mild, neutral conditions involving Cu[(S)-(R)-ppfa]Cl, AgNTf2, and alcohols. The dual additives of AgNTf2 and alcohols were found to play crucial roles for achieving high catalytic activity and enantio- and diastereoselectivity (up to 98% ee and 70:1 dr).

  15. Retention of heavy metals by carboxyl functional groups of biochars in small arms range soil

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Long-term effectiveness of biochar for heavy metal stabilization depends upon biochar’s sorptive property and recalcitrance in soil. To understand the role of carboxyl functional groups on heavy metal stabilization, cottonseed hull biochar and flax shive steam activated biochar having low O/C ratio...

  16. Social Resources and Change in Functional Health: Comparing Three Age Groups

    ERIC Educational Resources Information Center

    Randall, G. Kevin; Martin, Peter; Bishop, Alex J.; Johnson, Mary Ann; Poon, Leonard W.

    2012-01-01

    This study examined the mediating and moderating role of social resources on the association between age and change in functional health for three age groups of older adults. Data were provided by those in their 60s, 80s, and 100s who participated in the first two phases of the Georgia Centenarian study. Analyses confirmed the study's hypothesis…

  17. Neuropsychological Functioning in Specific Learning Disorders--Reading, Writing and Mixed Groups

    ERIC Educational Resources Information Center

    Kohli, Adarsh; Kaur, Manreet; Mohanty, Manju; Malhotra, Savita

    2006-01-01

    Aim: The study compared the pattern of deficits, intelligence and neuropsychological functioning in subcategories of learning disorders. Methods: Forty-six children (16 with reading disorders, 11 with writing disorders and 19 with both reading and writing disorders--mixed group) in the age range of 7-14 years were assessed using the NIMHANS Index…

  18. Group Social Skills Instruction for Adolescents with High-Functioning Autism Spectrum Disorders

    ERIC Educational Resources Information Center

    White, Susan W.; Koenig, Kathleen; Scahill, Lawrence

    2010-01-01

    Given the increased recognition of autism spectrum disorders (ASD) and the chronic and pervasive nature of associated deficits, there is a pressing need for effective treatments. The feasibility and preliminary efficacy of a structured, group social skills training program for high-functioning youth with ASD was examined in this study. Fifteen…

  19. Beta-WAIS Comparisons with Low Functioning Minority Group Offenders: A Cautionary Note.

    ERIC Educational Resources Information Center

    Hiltonsmith, Robert W.; And Others

    1982-01-01

    Investigated the utility of the Revised Beta as a screening device for low-functioning minority-group criminal offenders. Mean scores for this sample were correlated only mildly. This finding contradicts prior research and creates the need for caution in using the Beta as a screening device with this population. (Author)

  20. Group-Specific Effects of Matching Subtest Contamination on the Identification of Differential Item Functioning

    ERIC Educational Resources Information Center

    Keiffer, Elizabeth Ann

    2011-01-01

    A differential item functioning (DIF) simulation study was conducted to explore the type and level of impact that contamination had on type I error and power rates in DIF analyses when the suspect item favored the same or opposite group as the DIF items in the matching subtest. Type I error and power rates were displayed separately for the…

  1. Detection of Differential Item Functioning for More than Two Groups: A Monte Carlo Comparison of Methods

    ERIC Educational Resources Information Center

    Finch, W. Holmes

    2016-01-01

    Differential item functioning (DIF) assessment is a crucial component in test construction, serving as the primary way in which instrument developers ensure that measures perform in the same way for multiple groups within the population. When such is not the case, scores may not accurately reflect the trait of interest for all individuals in the…

  2. Detecting Native Language Group Differences at the Subskills Level of Reading: A Differential Skill Functioning Approach

    ERIC Educational Resources Information Center

    Li, Hongli; Suen, Hoi K.

    2013-01-01

    Differential skill functioning (DSF) exists when examinees from different groups have different probabilities of successful performance in a certain subskill underlying the measured construct, given that they have the same ability on the overall construct. Using a DSF approach, this study examined the differences between two native language…

  3. A FUNCTIONAL GROUP CHARACTERIZATION OF ORGANIC PM 2.5 EXPOSURE: RESULTS FROM THE RIOPA STUDY

    EPA Science Inventory

    The functional group (FG) composition of urban residential outdoor, indoor, and personal fine particle (PM2.5) samples is presented and used to provide insights relevant to organic PM2.5 exposure. PM2.5 samples (48 h) were collected during the Rel...

  4. Unitary representations of three dimensional Lie groups revisited: A short tutorial via harmonic functions

    NASA Astrophysics Data System (ADS)

    Campoamor-Stursberg, R.; Rausch de Traubenberg, M.

    2017-04-01

    The representation theory of three dimensional real and complex Lie groups is reviewed from the perspective of harmonic functions defined over certain appropriate manifolds. An explicit construction of all unitary representations is given. The realisations obtained are shown to be related with each other by either natural operations as real forms or Inönü-Wigner contractions.

  5. Chemkarta: A Card Game for Teaching Functional Groups in Undergraduate Organic Chemistry

    ERIC Educational Resources Information Center

    Knudtson, Christopher A.

    2015-01-01

    Students in undergraduate organic chemistry courses are frequently overwhelmed by the volume and complexity of information they are expected to learn. To aid in students' learning of organic functional groups, a novel card game "ChemKarta" is reported that can serve as a useful alternative to flashcards. This pedagogy is a simple…

  6. IMPORTANCE OF ACTIVATED CARBON'S OXYGEN SURFACE FUNCTIONAL GROUPS ON ELEMENTAL MERCURY ADSORPTION

    EPA Science Inventory

    The effect of varying physical and chemical properties of activated carbons on adsorption of elemental mercury [Hg(0)] was studied by treating two activated carbons to modify their surface functional groups and pore structures. Heat treatment (1200 K) in nitrogen (N2), air oxidat...

  7. 14 CFR 10 - Functional Classification-Operating Expenses of Group I Air Carriers

    Code of Federal Regulations, 2012 CFR

    2012-01-01

    ... 14 Aeronautics and Space 4 2012-01-01 2012-01-01 false Functional Classification-Operating Expenses of Group I Air Carriers Section 10 Section Section 10 Aeronautics and Space OFFICE OF THE SECRETARY, DEPARTMENT OF TRANSPORTATION (AVIATION PROCEEDINGS) ECONOMIC REGULATIONS UNIFORM SYSTEM OF ACCOUNTS AND REPORTS FOR LARGE CERTIFICATED AIR...

  8. Review of Social Skills Training Groups for Youth with Asperger Syndrome and High Functioning Autism

    ERIC Educational Resources Information Center

    Cappadocia, M. Catherine; Weiss, Jonathan A.

    2011-01-01

    Although social skills deficits represent core symptoms of Asperger Syndrome and High Functioning Autism, there is limited research investigating the empirical validity of social skills interventions currently being used with these populations. This literature review compares three types of social skills training groups: traditional, cognitive…

  9. Urinary Cortisol Circadian Rhythm in a Group of High-Functioning Children with Autism.

    ERIC Educational Resources Information Center

    Richdale, Amanda L.; Prior, Margot R.

    1992-01-01

    This study found no evidence for abnormal temporal placement of the basal urinary cortisol circadian rhythm in a group of 18 high-functioning children (ages 4-14) with autism. There was a tendency toward cortisol hypersecretion during the day, predominantly in autistic children who were integrated into the normal school system. (Author/JDD)

  10. An Epistemological Inquiry into Organic Chemistry Education: Exploration of Undergraduate Students' Conceptual Understanding of Functional Groups

    ERIC Educational Resources Information Center

    Akkuzu, Nalan; Uyulgan, Melis Arzu

    2016-01-01

    This study sought to determine the levels of conceptual understanding of undergraduate students regarding organic compounds within different functional groups. A total of 60 students who were enrolled in the Department of Secondary Science and Mathematics Education of a Faculty of Education at a state university in Turkey and who had followed an…

  11. Class-Wide Function-Related Intervention Teams: Effects of Group Contingency Programs in Urban Classrooms

    ERIC Educational Resources Information Center

    Kamps, Debra; Wills, Howard P.; Heitzman-Powell, Linda; Laylin, Jeff; Szoke, Carolyn; Petrillo, Tai; Culey, Amy

    2011-01-01

    The purpose of the study was to determine the effectiveness of the Class-Wide Function-related Intervention Teams (CW-FIT) program, a group contingency intervention for whole classes, and for students with disruptive behaviors who are at risk for emotional/behavioral disorders (EBD). The CW-FIT program includes four elements designed from…

  12. Refinements to the structure of graphite oxide: absolute quantification of functional groups via selective labelling.

    PubMed

    Eng, Alex Yong Sheng; Chua, Chun Kiang; Pumera, Martin

    2015-12-21

    Chemical modification and functionalization of inherent functional groups within graphite oxide (GO) are essential aspects of graphene-based nano-materials used in wide-ranging applications. Despite extensive research, there remains some discrepancy in its structure, with current knowledge limited primarily to spectroscopic data from XPS, NMR and vibrational spectroscopies. We report herein an innovative electrochemistry-based approach. Four electroactive labels are chosen to selectively functionalize groups in GO, and quantification of each group is achieved by voltammetric analysis. This allows for the first time quantification of absolute amounts of each group, with a further advantage of distinguishing various carbonyl species: namely ortho- and para-quinones from aliphatic ketones. Intrinsic variations in the compositions of permanganate versus chlorate-oxidized GOs were thus observed. Principal differences include permanganate-GO exhibiting substantial quinonyl content, in comparison to chlorate-GO with the vast majority of its carbonyls as isolated ketones. The results confirm that carboxylic groups are rare in actuality, and are in fact entirely absent from chlorate-GO. These observations refine and advance our understanding of GO structure by addressing certain disparities in past models resulting from employment of different oxidation routes, with the vital implication that GO production methods cannot be used interchangeably in the manufacture of graphene-based devices.

  13. Increased acetyl group availability enhances contractile function of canine skeletal muscle during ischemia.

    PubMed Central

    Timmons, J A; Poucher, S M; Constantin-Teodosiu, D; Worrall, V; Macdonald, I A; Greenhaff, P L

    1996-01-01

    Skeletal muscle contractile function is impaired during acute ischemia such as that experienced by peripheral vascular disease patients. We therefore, examined the effects of dichloroacetate, which can alter resting metabolism, on canine gracilis muscle contractile function during constant flow ischemia. Pretreatment with dichloroacetate increased resting pyruvate dehydrogenase complex activity and resting acetylcarnitine concentration by approximately 4- and approximately 10-fold, respectively. After 20-min contraction the control group had demonstrated an approximately 40% reduction in isomeric tension whereas the dichloroacetate group had fatigued by approximately 25% (P < 0.05). Dichloroacetate resulted in less lactate accumulation (10.3 +/- 3.0 vs 58.9 +/- 10.5 mmol.kg-1 dry muscle [dm], P < 0.05) and phosphocreatine hydrolysis (15.6 +/- 6.3 vs 33.8 +/- 9.0 mmol.kg-1 dm, P < 0.05) during contraction. Acetylcarnitine concentration fell during contraction by 5.4 +/- 1.8 mmol.kg-1 dm in the dichloroacetate group but increased by 10.0 +/- 1.9 mmol.kg-1 dm in the control group. In conclusion, dichloroacetate enhanced contractile function during ischemia, independently of blood flow, such that it appears oxidative ATP regeneration is limited by pyruvate dehydrogenase complex activity and acetyl group availability. PMID:8609248

  14. Functional group analysis of natural organic colloids and clay association kinetics using C(1s) spectromicroscopy

    NASA Astrophysics Data System (ADS)

    Schäfer, T.; Hertkorn, N.; Artinger, R.; Claret, F.; Bauer, A.

    2003-03-01

    The quantification of natural humic colloid functional group content and chemical association of humic substances with clay minerals exerts a crucial role in the colloid-borne mobility of actinides due to the functional group dependent strong interaction with multivalent metal ions. Functional group quantification in isolated fulvic acids of the Gorleben groundwater (Lower Saxony, NW Germany) by comparison of high resolution C(1s) NEXAFS spectra deconvolution with ^{13}C-NMR measurements showed good correlation (r^2> 0.9) and gives a potential quantification tool in complex natural groundwater Systems. Time resolved soft X-ray spectromicroscopy on dissolved organic carbon stabilized SWy-2 smectite colloids revealed an enrichment of carboxyl groups on broken edges (silanol/aluminol groups) at short contact times (1h). With longer contact times (7d, 6 months) the clay associated organic carbon increases and significantly higher aromatic content associated with basal surfaces were detected. The enhanced sorption of aromatic compounds can be related to an increase in mineral surface hydrophobicity and/or preferential sorption on charged siloxane surfaces.

  15. Organic functional group transformations in water at elevated temperature and pressure: Reversibility, reactivity, and mechanisms

    NASA Astrophysics Data System (ADS)

    Shipp, Jessie; Gould, Ian R.; Herckes, Pierre; Shock, Everett L.; Williams, Lynda B.; Hartnett, Hilairy E.

    2013-03-01

    Many transformation reactions involving hydrocarbons occur in the presence of H2O in hydrothermal systems and deep sedimentary systems. We investigate these reactions using laboratory-based organic chemistry experiments at high temperature and pressure (300 °C and 100 MPa). Organic functional group transformation reactions using model organic compounds based on cyclohexane with one or two methyl groups provided regio- and stereochemical markers that yield information about reversibility and reaction mechanisms. We found rapidly reversible interconversion between alkanes, alkenes, dienes, alcohols, ketones, and enones. The alkane-to-ketone reactions were not only completely reversible, but also exhibited such extensive reversibility that any of the functional groups along the reaction path (alcohol, ketone, and even the diene) could be used as the reactant and form all the other groups as products. There was also a propensity for these ring-based structures to dehydrogenate; presumably from the alkene, through a diene, to an aromatic ring. The product suites provide strong evidence that water behaved as a reactant and the various functional groups showed differing degrees of reactivity. Mechanistically-revealing products indicated reaction mechanisms that involve carbon-centered cation intermediates. This work therefore demonstrates that a wide range of organic compound types can be generated by abiotic reactions at hydrothermal conditions.

  16. Electronic and optical response of Ru(II) complexes functionalized by methyl, carboxylate groups: joint theoretical and experimental study

    SciTech Connect

    Tretiak, Sergei

    2008-01-01

    New photovoltaic and photocatalysis applications have been recently proposed based on the hybrid Ru(II)-bipyridine-complex/semiconductor quantum dot systems. In order to attach the complex to the surface of a semiconductor, a linking bridge - a carboxyl group - is added to one or two of the 2,2{prime}-bipyridine ligands. Such changes in the ligand structure, indeed, affect electronic and optical properties and consequently, the charge transfer reactivity of Ru-systems. In this study, we apply both theoretical and experimental approaches to analyze the effects brought by functionalization of bipyridine ligands with the methyl, carboxyl, and carboxilate groups on the electronic structure and optical response of the Ru(II) bipyridine complex. First principle calculations based on density functional theory (DFT) and linear response time dependent density functional theory (TDDFT) are used to simulate the ground and excited-state structures of functionalized Ru-complexes in the gas phase, as well as in acetonitrile solution. In addition, an inelaborate Frenkel exciton model is used to explain the optical activity and splitting patterns of the low-energy excited states. All theoretical results nicely complement experimental absorption spectra of Ru-complexes and contribute to their interpretation. We found that the carboxyl group breaks the degeneracy of two low-energy optically bright excited states and red-shifts the absorption spectrum, while leaves ionization and affinity energies of complexes almost unchanged. Experimental studies show a high probability of deprotonation of the carbboxyl group in the Ru-complexes resulted in a slight blue shift and decrease of intensities of the low energy absorption peaks. Comparison of experimental and theoretical linear response spectra of deprotanated complexes demonstrate strong agreement when acetonitrile solvent is used in simulations. A polar solvent is found to play an important role in calculations of optical spectra: it

  17. An analytical approach to the problem of inverse optimization with additive objective functions: an application to human prehension.

    PubMed

    Terekhov, Alexander V; Pesin, Yakov B; Niu, Xun; Latash, Mark L; Zatsiorsky, Vladimir M

    2010-09-01

    We consider the problem of what is being optimized in human actions with respect to various aspects of human movements and different motor tasks. From the mathematical point of view this problem consists of finding an unknown objective function given the values at which it reaches its minimum. This problem is called the inverse optimization problem. Until now the main approach to this problems has been the cut-and-try method, which consists of introducing an objective function and checking how it reflects the experimental data. Using this approach, different objective functions have been proposed for the same motor action. In the current paper we focus on inverse optimization problems with additive objective functions and linear constraints. Such problems are typical in human movement science. The problem of muscle (or finger) force sharing is an example. For such problems we obtain sufficient conditions for uniqueness and propose a method for determining the objective functions. To illustrate our method we analyze the problem of force sharing among the fingers in a grasping task. We estimate the objective function from the experimental data and show that it can predict the force-sharing pattern for a vast range of external forces and torques applied to the grasped object. The resulting objective function is quadratic with essentially non-zero linear terms.

  18. An analytical approach to the problem of inverse optimization with additive objective functions: an application to human prehension

    PubMed Central

    Pesin, Yakov B.; Niu, Xun; Latash, Mark L.

    2010-01-01

    We consider the problem of what is being optimized in human actions with respect to various aspects of human movements and different motor tasks. From the mathematical point of view this problem consists of finding an unknown objective function given the values at which it reaches its minimum. This problem is called the inverse optimization problem. Until now the main approach to this problems has been the cut-and-try method, which consists of introducing an objective function and checking how it reflects the experimental data. Using this approach, different objective functions have been proposed for the same motor action. In the current paper we focus on inverse optimization problems with additive objective functions and linear constraints. Such problems are typical in human movement science. The problem of muscle (or finger) force sharing is an example. For such problems we obtain sufficient conditions for uniqueness and propose a method for determining the objective functions. To illustrate our method we analyze the problem of force sharing among the fingers in a grasping task. We estimate the objective function from the experimental data and show that it can predict the force-sharing pattern for a vast range of external forces and torques applied to the grasped object. The resulting objective function is quadratic with essentially non-zero linear terms. PMID:19902213

  19. A meta-analysis of functional group responses to forest recovery outside of the tropics.

    PubMed

    Spake, Rebecca; Ezard, Thomas H G; Martin, Philip A; Newton, Adrian C; Doncaster, C Patrick

    2015-12-01

    Both active and passive forest restoration schemes are used in degraded landscapes across the world to enhance biodiversity and ecosystem service provision. Restoration is increasingly also being implemented in biodiversity offset schemes as compensation for loss of natural habitat to anthropogenic development. This has raised concerns about the value of replacing old-growth forest with plantations, motivating research on biodiversity recovery as forest stands age. Functional diversity is now advocated as a key metric for restoration success, yet it has received little analytical attention to date. We conducted a meta-analysis of 90 studies that measured differences in species richness for functional groups of fungi, lichens, and beetles between old-growth control and planted or secondary treatment forests in temperate, boreal, and Mediterranean regions. We identified functional-group-specific relationships in the response of species richness to stand age after forest disturbance. Ectomycorrhizal fungi averaged 90 years for recovery to old-growth values (between 45 years and unrecoverable at 95% prediction limits), and epiphytic lichens took 180 years to reach 90% of old-growth values (between 140 years and never for recovery to old-growth values at 95% prediction limits). Non-saproxylic beetle richness, in contrast, decreased as stand age of broadleaved forests increased. The slow recovery by some functional groups essential to ecosystem functioning makes old-growth forest an effectively irreplaceable biodiversity resource that should be exempt from biodiversity offsetting initiatives.

  20. Structural and functional evolution of the P2Y12-like receptor group

    PubMed Central

    Hermsdorf, Thomas; Engemaier, Eva; Engel, Kathrin; Liebscher, Ines; Thor, Doreen; Zierau, Klaas; Römpler, Holger; Schulz, Angela

    2007-01-01

    Metabotropic pyrimidine and purine nucleotide receptors (P2Y receptors) belong to the superfamily of G protein-coupled receptors (GPCR). They are distinguishable from adenosine receptors (P1) as they bind adenine and/or uracil nucleotide triphosphates or diphosphates depending on the subtype. Over the past decade, P2Y receptors have been cloned from a variety of tissues and species, and as many as eight functional subtypes have been characterized. Most recently, several members of the P2Y12-like receptor group, which includes the clopidogrel-sensitive ADP receptor P2Y12, have been deorphanized. The P2Y12-like receptor group comprises several structurally related GPCR which, however, display heterogeneous agonist specificity including nucleotides, their derivatives, and lipids. Besides the established function of P2Y12 in platelet activation, expression in macrophages, neuronal and glial cells as well as recent results from functional studies implicate that several members of this group may have specific functions in neurotransmission, inflammation, chemotaxis, and response to tissue injury. This review focuses specifically on the structure-function relation and shortly summarizes some aspects of the physiological relevance of P2Y12-like receptor members. PMID:18404440

  1. The Dragonfly Nearby Galaxies Survey. III. The Luminosity Function of the M101 Group

    NASA Astrophysics Data System (ADS)

    Danieli, Shany; van Dokkum, Pieter; Merritt, Allison; Abraham, Roberto; Zhang, Jielai; Karachentsev, I. D.; Makarova, L. N.

    2017-03-01

    We obtained follow-up HST observations of the seven low surface brightness galaxies discovered with the Dragonfly Telephoto Array in the field of the massive spiral galaxy M101. Out of the seven galaxies, only three were resolved into stars and are potentially associated with the M101 group at D = 7 Mpc. Based on HST ACS photometry in the broad F606W and F814W filters, we use a maximum likelihood algorithm to locate the Tip of the Red Giant Branch in galaxy color–magnitude diagrams. Distances are {6.38}-0.35+0.35,{6.87}-0.30+0.21 and {6.52}-0.27+0.25 {Mpc} and we confirm that they are members of the M101 group. Combining the three confirmed low-luminosity satellites with previous results for brighter group members, we find the M101 galaxy group to be a sparsely populated galaxy group consisting of seven group members, down to M V = ‑9.2 mag. We compare the M101 cumulative luminosity function to that of the Milky Way and M31. We find that they are remarkably similar; in fact, the cumulative luminosity function of the M101 group gets even flatter for fainter magnitudes, and we show that the M101 group might exhibit the two known small-scale flaws in the ΛCDM model, namely “the missing satellite” problem and the “too big to fail” problem. Kinematic measurements of M101's satellite galaxies are required to determine whether the “too big to fail” problem does in fact exist in the M101 group.

  2. Ionization behavior, stoichiometry of association, and accessibility of functional groups in the active layers of reverse osmosis and nanofiltration membranes.

    PubMed

    Coronell, Orlando; González, Mari I; Mariñas, Benito J; Cahill, David G

    2010-09-01

    We characterized the fully aromatic polyamide (PA) active layers of six commercial reverse osmosis (RO) and nanofiltration (NF) membranes and found that in contrast to their similar elemental composition, total concentration of functional groups, and degree of polymerization, the ionization behavior and spatial distribution of carboxylic (R-COOH) groups within the active layers can be significantly different. We also studied the steric effects experienced by barium ion (Ba2+) in the active layers by determining the fraction of carboxylate (R-COO-) groups accessible to Ba2+; such fraction, referred to as the accessibility ratio (AR), was found to vary within the range AR=0.40-0.81, and to be generally independent of external solution pH. Additionally, we studied an NF membrane with a sulfonated polyethersulfone (SPES) active layer, and found that the concentration of sulfonate (R-SO3-) groups in the active layer was 1.67 M, independent of external solution pH and approximately three times higher than the maximum concentration (approximately 0.45+/-0.25 M) of R-COO- groups in PA active layers. The R-SO3- groups were found to be highly accessible to Ba2+ (AR=0.95+/-0.01).

  3. Effect of Habitat Size, Quality, and Isolation on Functional Groups of Beetles in Hollow Oaks

    PubMed Central

    Pilskog, Hanne Eik; Birkemoe, Tone; Framstad, Erik; Sverdrup-Thygeson, Anne

    2016-01-01

    One of the largest threats to biodiversity is land use change and habitat loss. Hollow oaks (Quercus spp. L.) are well-defined patches that are hotspots for biodiversity and red-listed species, but they are often rare and fragmented in the landscape. We investigated the effect of patch size, habitat quality, and isolation on functional groups and red-listed saproxylic beetles in hollow oaks (n = 40) in Norway. The groups were defined by host tree association, trophic grouping, and red-listed status. Habitat quality, represented by tree form was most important in explaining species richness for most groups. Patch size, represented by circumference and amount of dead branches, was most important in explaining abundance. Isolation, that is single oaks compared with oaks in groups, had a negative effect on the abundance of beetles feeding both on wood and fungi (xylomycethopagous), as well as on species associated with broadleaved trees (oak semi-specialists), but did not affect species richness. This indicates that at this scale and in this landscape, isolated oaks are as species rich and valuable for conservation as other oaks, although some functional groups may be more vulnerable to isolation than others. The red-listed species only responded to patch size, indicating that oaks with large circumference and many dead branches are especially important for red-listed species and for conservation. PMID:26945089

  4. Effect of Habitat Size, Quality, and Isolation on Functional Groups of Beetles in Hollow Oaks.

    PubMed

    Pilskog, Hanne Eik; Birkemoe, Tone; Framstad, Erik; Sverdrup-Thygeson, Anne

    2016-01-01

    One of the largest threats to biodiversity is land use change and habitat loss. Hollow oaks (Quercus spp. L.) are well-defined patches that are hotspots for biodiversity and red-listed species, but they are often rare and fragmented in the landscape. We investigated the effect of patch size, habitat quality, and isolation on functional groups and red-listed saproxylic beetles in hollow oaks (n = 40) in Norway. The groups were defined by host tree association, trophic grouping, and red-listed status. Habitat quality, represented by tree form was most important in explaining species richness for most groups. Patch size, represented by circumference and amount of dead branches, was most important in explaining abundance. Isolation, that is single oaks compared with oaks in groups, had a negative effect on the abundance of beetles feeding both on wood and fungi (xylomycethopagous), as well as on species associated with broadleaved trees (oak semi-specialists), but did not affect species richness. This indicates that at this scale and in this landscape, isolated oaks are as species rich and valuable for conservation as other oaks, although some functional groups may be more vulnerable to isolation than others. The red-listed species only responded to patch size, indicating that oaks with large circumference and many dead branches are especially important for red-listed species and for conservation.

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

    USGS Publications Warehouse

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

    2008-01-01

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

  6. Multi-regulator functional renormalization group for many-fermion systems

    NASA Astrophysics Data System (ADS)

    Tanizaki, Yuya; Hatsuda, Tetsuo

    We propose a method of multi-regulator functional renormalization group (MR-FRG) which is a novel formulation of functional renormalization group with multiple infrared (IR) regulators. It is applied to a two-component fermionic system with an attractive contact interaction to study crossover phenomena between the Bardeen-Cooper-Schrieffer (BCS) phase and the Bose-Einstein condensation (BEC) phase. To control both the fermionic one-particle excitations and the bosonic collective excitations, IR regulators are introduced, one for the fermionic two-point function and another for the four-fermion vertex. It is shown that the Nozières-Schmitt-Rink (NSR) theory, which is successful to capture qualitative features of the BCS-BEC crossover, can be derived from MR-FRG. Some aspects of MR-FRG to go beyond the NSR theory are also discussed.

  7. Quantification of protein group coherence and pathway assignment using functional association

    PubMed Central

    2011-01-01

    Background Genomics and proteomics experiments produce a large amount of data that are awaiting functional elucidation. An important step in analyzing such data is to identify functional units, which consist of proteins that play coherent roles to carry out the function. Importantly, functional coherence is not identical with functional similarity. For example, proteins in the same pathway may not share the same Gene Ontology (GO) terms, but they work in a coordinated fashion so that the aimed function can be performed. Thus, simply applying existing functional similarity measures might not be the best solution to identify functional units in omics data. Results We have designed two scores for quantifying the functional coherence by considering association of GO terms observed in two biological contexts, co-occurrences in protein annotations and co-mentions in literature in the PubMed database. The counted co-occurrences of GO terms were normalized in a similar fashion as the statistical amino acid contact potential is computed in the protein structure prediction field. We demonstrate that the developed scores can identify functionally coherent protein sets, i.e. proteins in the same pathways, co-localized proteins, and protein complexes, with statistically significant score values showing a better accuracy than existing functional similarity scores. The scores are also capable of detecting protein pairs that interact with each other. It is further shown that the functional coherence scores can accurately assign proteins to their respective pathways. Conclusion We have developed two scores which quantify the functional coherence of sets of proteins. The scores reflect the actual associations of GO terms observed either in protein annotations or in literature. It has been shown that they have the ability to accurately distinguish biologically relevant groups of proteins from random ones as well as a good discriminative power for detecting interacting pairs of

  8. Functional renormalization group approach for inhomogeneous one-dimensional Fermi systems with finite-ranged interactions

    NASA Astrophysics Data System (ADS)

    Weidinger, Lukas; Bauer, Florian; von Delft, Jan

    2017-01-01

    We introduce an equilibrium formulation of the functional renormalization group (fRG) for inhomogeneous systems capable of dealing with spatially finite-ranged interactions. In the general third-order truncated form of fRG, the dependence of the two-particle vertex is described by O (N4) independent variables, where N is the dimension of the single-particle system. In a previous paper [Bauer et al., Phys. Rev. B 89, 045128 (2014), 10.1103/PhysRevB.89.045128], the so-called coupled-ladder approximation (CLA) was introduced and shown to admit a consistent treatment for models with a purely onsite interaction, reducing the vertex to O (N2) independent variables. In this work, we introduce an extended version of this scheme, called the extended coupled ladder approximation (eCLA), which includes a spatially extended feedback between the individual channels, measured by a feedback length L , using O (N2L2) independent variables for the vertex. We apply the eCLA in a static approximation and at zero temperature to three types of one-dimensional model systems, focusing on obtaining the linear response conductance. First, we study a model of a quantum point contact (QPC) with a parabolic barrier top and on-site interactions. In our setup, where the characteristic length lx of the QPC ranges between approximately 4-10 sites, eCLA achieves convergence once L becomes comparable to lx. It also turns out that the additional feedback stabilizes the fRG flow. This enables us, second, to study the geometric crossover between a QPC and a quantum dot, again for a one-dimensional model with on-site interactions. Third, the enlarged feedback also enables the treatment of a finite-ranged interaction extending over up to L sites. Using a simple estimate for the form of such a finite-ranged interaction in a QPC with a parabolic barrier top, we study its effects on the conductance and the density. We find that for low densities and sufficiently large interaction ranges the conductance

  9. Taxonomy of the hyper-diverse ant genus Tetramorium Mayr in the Malagasy region (Hymenoptera, Formicidae, Myrmicinae) – first record of the T. setigerum species group and additions to the Malagasy species groups with an updated illustrated identification key

    PubMed Central

    Hita Garcia, Francisco; Fisher, Brian L.

    2015-01-01

    Abstract In this study we provide an update to the taxonomy of the ant genus Tetramorium Mayr in Madagascar. We report the first record of the Tetramorium setigerum species group in Madagascar and describe the only Malagasy representative as Tetramorium cavernicola sp. n., which is known only from a cave in Ankarana. In addition, we provide an overview of the 19 proposed Malagasy species groups, and discuss their zoogeography and relationships to other groups and larger lineages within the hyper-diverse genus Tetramorium. At present, we recognise a highly unique Malagasy Tetramorium fauna with 113 species endemic to the island of Madagascar out of a total of 125 translating into an endemism rate of 93%. We hypothesise that this fauna is based on one or a few colonisation events from the Afrotropical region, with subsequent adaptive radiation in Madagascar. Furthermore, we present an updated and illustrated identification key to the Tetramorium species groups in the Malagasy region. PMID:26257564

  10. Wetting properties of model interphases coated with defined organic functional groups

    NASA Astrophysics Data System (ADS)

    Woche, Susanne K.; Goebel, Marc-O.; Guggenberger, Georg; Tunega, Daniel; Bachmann, Joerg

    2013-04-01

    Surface properties of soil particles are of particular interest regarding transport of water and sorption of solutes, especially hazardous xenobiotic species. Wetting properties (e.g. determined by contact angle, CA), governed by the functional groups exposed, are crucial to understand sorption processes in water repellent soils as well as for the geometry of water films sustaining microbial processes on the pore scale. Natural soil particle surfaces are characterized by a wide variety of mineralogical and chemical compounds. Their composition is almost impossible to identify in full. Hence, in order to get a better understanding about surface properties, an option is the usage of defined model surfaces, whereas the created surface should be comparable to natural soil interphases. We exposed smooth glass surfaces to different silane compounds, resulting in a coating covalently bound to the surface and exhibiting defined organic functional groups towards the pore space. The wetting properties as evaluated by CA and the surface free energy (SFE), calculated according to the Acid-Base Theory, were found to be a function of the specific functional group. Specifically, the treated surfaces showed a large variation of CA and SFE as function of chain length and polarity of the organic functional group. The study of wetting properties was accompanied by XPS analysis for selective detection of chemical compounds of the interphase. As the reaction mechanism of the coating process is known, the resulting interphase structure can be modeled based on energetic considerations. A next step is to use same coatings for the defined modification of the pore surfaces of porous media to study transport and sorption processes in complex three phase systems.

  11. Benchmark calculations of excess electrons in water cluster cavities: balancing the addition of atom-centered diffuse functions versus floating diffuse functions.

    PubMed

    Zhang, Changzhe; Bu, Yuxiang

    2016-09-14

    Diffuse functions have been proved to be especially crucial for the accurate characterization of excess electrons which are usually bound weakly in intermolecular zones far away from the nuclei. To examine the effects of diffuse functions on the nature of the cavity-shaped excess electrons in water cluster surroundings, both the HOMO and LUMO distributions, vertical detachment energies (VDEs) and visible absorption spectra of two selected (H2O)24(-) isomers are investigated in the present work. Two main types of diffuse functions are considered in calculations including the Pople-style atom-centered diffuse functions and the ghost-atom-based floating diffuse functions. It is found that augmentation of atom-centered diffuse functions contributes to a better description of the HOMO (corresponding to the VDE convergence), in agreement with previous studies, but also leads to unreasonable diffuse characters of the LUMO with significant red-shifts in the visible spectra, which is against the conventional point of view that the more the diffuse functions, the better the results. The issue of designing extra floating functions for excess electrons has also been systematically discussed, which indicates that the floating diffuse functions are necessary not only for reducing the computational cost but also for improving both the HOMO and LUMO accuracy. Thus, the basis sets with a combination of partial atom-centered diffuse functions and floating diffuse functions are recommended for a reliable description of the weakly bound electrons. This work presents an efficient way for characterizing the electronic properties of weakly bound electrons accurately by balancing the addition of atom-centered diffuse functions and floating diffuse functions and also by balancing the computational cost and accuracy of the calculated results, and thus is very useful in the relevant calculations of various solvated electron systems and weakly bound anionic systems.

  12. Zooplankton functional groups on the continental shelf of the yellow sea

    NASA Astrophysics Data System (ADS)

    Sun, Song; Huo, Yuanzi; Yang, Bo

    2010-06-01

    Zooplankton plays a vital role in marine ecosystems. Variations in the zooplankton species composition, biomass, and secondary production will change the structure and function of the ecosystem. How to describe this process and make it easier to be modeled in the Yellow Sea ecosystem is the main purpose of this paper. The zooplankton functional groups approach, which is considered a good method of linking the structure of food webs and the energy flow in the ecosystems, is used to describe the main contributors of secondary produciton of the Yellow Sea ecosystem. The zooplankton can be classified into six functional groups: giant crustaceans, large copepods, small copepods, chaetognaths, medusae, and salps. The giant crustaceans, large copepods, and small copepods groups, which are the main food resources for fish, are defined depending on the size spectrum. Medusae and chaetognaths are the two gelatinous carnivorous groups, which compete with fish for food. The salps group, acting as passive filter-feeders, competes with other species feeding on phytoplankton, but their energy could not be efficiently transferred to higher trophic levels. From the viewpoint of biomass, which is the basis of the food web, and feeding activities, the contributions of each functional group to the ecosystem were evaluated; the seasonal variations, geographical distribution patterns, and species composition of each functional group were analyzed. The average zooplankton biomass was 2.1 g dry wt m -2 in spring, to which the giant crustaceans, large copepods, and small copepods contributed 19, 44, and 26%, respectively. High biomasses of the large copepods and small copepods were distributed at the coastal waters, while the giant crustaceans were mainly located at offshore area. In summer, the mean biomass was 3.1 g dry wt m -2, which was mostly contributed by the giant crustaceans (73%), and high biomasses of the giant crustaceans, large copepods, and small copepods were all distributed

  13. Effect of Additives on Green Sand Molding Properties using Design of Experiments and Taguchi's Quality Loss Function - An Experimental Study

    NASA Astrophysics Data System (ADS)

    Desai, Bhagyashree; Mokashi, Pavani; Anand, R. L.; Burli, S. B.; Khandal, S. V.

    2016-09-01

    The experimental study aims to underseek the effect of various additives on the green sand molding properties as a particular combination of additives could yield desired sand properties. The input parameters (factors) selected were water and powder (Fly ash, Coconut shell and Tamarind) in three levels. Experiments were planned using design of experiments (DOE). On the basis of plans, experiments were conducted to understand the behavior of sand mould properties such as compression strength, shear strength, permeability number with various additives. From the experimental results it could be concluded that the factors have significant effect on the sand properties as P-value found to be less than 0.05 for all the cases studied. The optimization based on quality loss function was also performed. The study revealed that the quality loss associated with the tamarind powder was lesser compared to other additives selected for the study. The optimization based on quality loss function and the parametric analysis using ANOVA suggested that the tamarind powder of 8 gm per Kg of molding sand and moisture content of 7% yield better properties to obtain sound castings.

  14. The effect of affective bibliotherapy on clients' functioning in group therapy.

    PubMed

    Shechtman, Zipora; Nir-Shfrir, Rivka

    2008-01-01

    Abstract The effect of affective group bibliotherapy (GB) was compared to affective group therapy (GT) on patients' functioning in therapy and their session impression. Three small groups totaling twenty-five in-patients in a hospital in Israel participated in the study. Clients concurrently participated in both group types, undergoing three sessions in each condition. In-therapy behaviors were assessed through the Client Behavior System (CBS; Hill & O'Brien, 1999). Results indicated that in the GB condition compared to the GT condition, clients showed less resistance, used simple responses less frequently, and expressed greater affective exploration. The Session Evaluation Questionnaire (SEQ; Stiles et al., 1994) was used to measure clients' impressions of the sessions. Results indicated that patients evaluated the two treatment conditions equally. Overall, the results support earlier findings, suggesting that affective bibliotherapy can be an effective method of treatment.

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

    SciTech Connect

    Fifield, Leonard S.; Grate, Jay W.

    2010-06-01

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

  16. Kelvin-probe force microscopy of the pH-dependent charge of functional groups

    NASA Astrophysics Data System (ADS)

    Stone, Alexander D. D.; Mesquida, Patrick

    2016-06-01

    Kelvin-probe Force Microscopy (KFM) is an established method to map surface potentials or surface charges at high, spatial resolution. However, KFM does not work in water, which restricts its applicability considerably, especially when considering common, functional chemical groups in biophysics such as amine or carboxy groups, whose charge depends on pH. Here, we demonstrate that the KFM signal of such groups taken in air after exposure to water correlates qualitatively with their expected charge in water for a wide range of pH values. The correlation was tested with microcontact-printed thiols exposing amine and carboxy groups. Furthermore, it was shown that collagen fibrils, as an example of a biological material, exhibit a particular, pH-sensitive surface charge pattern, which could be caused by the particular arrangement of ionizable residues on the collagen fibril surface.

  17. Matrix intensification alters avian functional group composition in adjacent rainforest fragments.

    PubMed

    Deikumah, Justus P; McAlpine, Clive A; Maron, Martine

    2013-01-01

    Conversion of farmland land-use matrices to surface mining is an increasing threat to the habitat quality of forest remnants and their constituent biota, with consequences for ecosystem functionality. We evaluated the effects of matrix type on bird community composition and the abundance and evenness within avian functional groups in south-west Ghana. We hypothesized that surface mining near remnants may result in a shift in functional composition of avifaunal communities, potentially disrupting ecological processes within tropical forest ecosystems. Matrix intensification and proximity to the remnant edge strongly influenced the abundance of members of several functional guilds. Obligate frugivores, strict terrestrial insectivores, lower and upper strata birds, and insect gleaners were most negatively affected by adjacent mining matrices, suggesting certain ecosystem processes such as seed dispersal may be disrupted by landscape change in this region. Evenness of these functional guilds was also lower in remnants adjacent to surface mining, regardless of the distance from remnant edge, with the exception of strict terrestrial insectivores. These shifts suggest matrix intensification can influence avian functional group composition and related ecosystem-level processes in adjacent forest remnants. The management of matrix habitat quality near and within mine concessions is important for improving efforts to preserveavian biodiversity in landscapes undergoing intensification such as through increased surface mining.

  18. Photochemical and antimicrobial properties of silver nanoparticle-encapsulated chitosan functionalized with photoactive groups.

    PubMed

    Mathew, Thomas V; Kuriakose, Sunny

    2013-10-01

    Chitosan was functionalized with 4-((E)-2-(3-hydroxynaphthalen-2-yl)diazen-1-yl)benzoic acid by the coupling of the hydroxyl functional groups of chitosan with carboxylic acid group of the dye by DCC coupling method. The silver nanoparticles were prepared by sol-gel method of nanoparticle synthesis. Silver nanoparticle-encapsulated functionalized chitosan was prepared by the phase transfer method. The products were characterized by FTIR, UV-Vis, fluorescence and NMR spectroscopic methods and by SEM and TEM analysis. The photochemical properties of silver nanoparticle-encapsulated chitosan functionalized with 4-((E)-2-(3-hydroxynaphthalen-2-yl)diazen-1-yl)benzoic acid was studied in detail. The light-fastening properties of the chromophoric system was enhanced when attached to chitosan, and it can be further improved by the encapsulation of silver nanoparticles. The antibacterial analysis of silver nanoparticle-encapsulated functionalized chitosan was carried out against Staphylococcus aureus and Escherichia coli and against fungal species such as Aspergillus flavus and Aspergillus terreus. This study showed that silver nanoparticles-encapsulated functionalized chitosan can be used for antibacterial and antifungal applications.

  19. Modifications of chemical functional groups of Pandanus amaryllifolius Roxb and its effect towards biosorption of heavy metals

    NASA Astrophysics Data System (ADS)

    Abdullah, Mohd. Zamri; Ismail, Siti Salwa

    2015-07-01

    The utilization of non-living biomass as an alternative biosorbent for heavy metal removal has gain a tremendous consideration through the years. Pandanus amaryllifolius Roxb or pandan leaves, which is widely used as food additives in the South East Asia region, has been selected for its viability in the said effort due to the presence of chemical functional groups on its cellular network that enables the sorption to occur. In order to elucidate the possible mechanisms participated during the heavy metal removal process, the biosorbent undergone a series of modification techniques to alter the chemical functional groups present on its constituent. From the outcome of the chemically-modified biosorbent being subjected to the contact with metal cations, nitrogen- and oxygen-containing groups present on the biosorbent are believed to be responsible for the metal uptake to occur through complexation mechanism. Modifying amine groups causes 14% reduction of Cu(II) uptake, whereas removing protein element increases the uptake to 26% as compared to the unmodified biosorbent. Also, scanning electron micrographs further suggested that the adsorption mechanism could perform in parallel, as attributed to the evidence of porous structure throughout the biosorbent fibrous nature.

  20. Modifications of chemical functional groups of Pandanus amaryllifolius Roxb and its effect towards biosorption of heavy metals

    SciTech Connect

    Abdullah, Mohd Zamri Ismail, Siti Salwa

    2015-07-22

    The utilization of non-living biomass as an alternative biosorbent for heavy metal removal has gain a tremendous consideration through the years. Pandanus amaryllifolius Roxb or pandan leaves, which is widely used as food additives in the South East Asia region, has been selected for its viability in the said effort due to the presence of chemical functional groups on its cellular network that enables the sorption to occur. In order to elucidate the possible mechanisms participated during the heavy metal removal process, the biosorbent undergone a series of modification techniques to alter the chemical functional groups present on its constituent. From the outcome of the chemically-modified biosorbent being subjected to the contact with metal cations, nitrogen- and oxygen-containing groups present on the biosorbent are believed to be responsible for the metal uptake to occur through complexation mechanism. Modifying amine groups causes 14% reduction of Cu(II) uptake, whereas removing protein element increases the uptake to 26% as compared to the unmodified biosorbent. Also, scanning electron micrographs further suggested that the adsorption mechanism could perform in parallel, as attributed to the evidence of porous structure throughout the biosorbent fibrous nature.

  1. Refinements to the structure of graphite oxide: absolute quantification of functional groups via selective labelling

    NASA Astrophysics Data System (ADS)

    Eng, Alex Yong Sheng; Chua, Chun Kiang; Pumera, Martin

    2015-11-01

    Chemical modification and functionalization of inherent functional groups within graphite oxide (GO) are essential aspects of graphene-based nano-materials used in wide-ranging applications. Despite extensive research, there remains some discrepancy in its structure, with current knowledge limited primarily to spectroscopic data from XPS, NMR and vibrational spectroscopies. We report herein an innovative electrochemistry-based approach. Four electroactive labels are chosen to selectively functionalize groups in GO, and quantification of each group is achieved by voltammetric analysis. This allows for the first time quantification of absolute amounts of each group, with a further advantage of distinguishing various carbonyl species: namely ortho- and para-quinones from aliphatic ketones. Intrinsic variations in the compositions of permanganate versus chlorate-oxidized GOs were thus observed. Principal differences include permanganate-GO exhibiting substantial quinonyl content, in comparison to chlorate-GO with the vast majority of its carbonyls as isolated ketones. The results confirm that carboxylic groups are rare in actuality, and are in fact entirely absent from chlorate-GO. These observations refine and advance our understanding of GO structure by addressing certain disparities in past models resulting from employment of different oxidation routes, with the vital implication that GO production methods cannot be used interchangeably in the manufacture of graphene-based devices.Chemical modification and functionalization of inherent functional groups within graphite oxide (GO) are essential aspects of graphene-based nano-materials used in wide-ranging applications. Despite extensive research, there remains some discrepancy in its structure, with current knowledge limited primarily to spectroscopic data from XPS, NMR and vibrational spectroscopies. We report herein an innovative electrochemistry-based approach. Four electroactive labels are chosen to selectively

  2. Quantity of Hydrophobic Functional CH-Groups - Decisive for Soil Water Repellency Caused by Digestate Amendment

    NASA Astrophysics Data System (ADS)

    Voelkner, Amrei; Holthusen, Dörthe; Ellerbrock, Ruth H.; Horn, Rainer

    2015-04-01

    Anaerobic digestates are used as organic fertilizers; however, they are suspected to interfere negatively with soils. To investigate the relevance of the anaerobic digestates composition on potential wettability and contact angle of the soil, we mixed in a laboratory experiment 30 m³ ha-1 of anaerobic digestates derived from mechanically pre-treated substrates from maize and sugar beet with a homogenized Cambic Luvisol. Fourier transform infrared-spectra and diffuse reflectance infrared Fourier transform-spectra of particle intact and finely ground soilanaerobic digestates-mixtures were analyzed to determine the quantities of hydrophobic functional groups in the soil-anaerobic digestates-mixtures that are used here as an indicator for the potential hydrophobicity. The anaerobic digestates application increased the amount of hydrophobic functional groups of the mixtures and reduced the wettability of the soil. However, for intact particle samples an up to threefold higher amount of hydrophobic groups was found as compared to the finely ground ones, indicating a dilution effect of mechanical grinding on the effectivity of the organic matter that is presumably located as a coating on mineral soil particles. For the particle intact samples, the intensity of hydrophobic functional groups bands denoting hydrophobic brickstones in organic matter is indicative for the actual wettability of the soil-anaerobic digestates-mixtures.

  3. Carboxylic acid functional group analysis using constant neutral loss scanning-mass spectrometry.

    PubMed

    Dron, Julien; Eyglunent, Gregory; Temime-Roussel, Brice; Marchand, Nicolas; Wortham, Henri

    2007-12-12

    The present study describes the development of a new analytical technique for the functional group determination of the carboxylic moiety using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS/MS) operated in the constant neutral loss scanning (CNLS) mode. Carboxylic groups were first derivatized into their corresponding methyl esters by reacting with BF3/methanol mix and the reaction mixture was then directly injected into the APCI chamber. The loss of methanol (m/z = 32 amu) resulting from the fragmentation of the protonated methyl esters was then monitored. Applying this method together with a statistical approach to reference mixtures containing 31 different carboxylic acids at randomly calculated concentrations demonstrated its suitability for quantitative functional group measurements with relative standard deviations below 15% and a detection limit of 0.005 mmol L(-1). Its applicability to environmental matrices was also shown through the determination of carboxylic acid concentrations inside atmospheric aerosol samples. To the best of our knowledge, it is the first time that the tandem mass spectrometry was successfully applied to functional group analysis, offering great perspectives in the characterization of complex mixtures which are prevailing in the field of environmental analysis as well as in the understanding of the chemical processes occurring in these matrices.

  4. Functional groups affect physical and biological properties of dextran-based hydrogels.

    PubMed

    Sun, Guoming; Shen, Yu-I; Ho, Chia Chi; Kusuma, Sravanti; Gerecht, Sharon

    2010-06-01

    Modification of dextran backbone allows the development of a hydrogel with specific characteristics. To enhance their functionality for tissue-engineered scaffolds, a series of dextran-based macromers was synthesized by incorporating various functional groups, including allyl isocyanate (Dex-AI), ethylamine (Dex-AE), chloroacetic acid (Dex-AC), or maleic-anhydride (Dex-AM) into dextrans. The dextran-based biodegradable hybrid hydrogels are developed by integrating polyethylene glycol diacrylate (PEGDA). To explore the effect of different derivatives on hydrogel properties, three different ratios of Dex/PEGDA are examined: low (20/80), medium (40/60), and high (60/40). Differences in physical and biological properties of the hydrogels are found, including swelling, degradation rate, mechanics, crosslinking density, biocompatibility (in vitro and in vivo), and vascular endothelial growth factor release. The results also indicate that the incorporation of amine groups into dextran gives rise to hydrogels with better biocompatible and release properties. We, therefore, conclude that the incorporation of different functional groups affects the fundamental properties of a dextran-based hydrogel network, and that amine groups are preferred to generate hydrogels for biomedical use.

  5. Functional characterization and phylogenetic analysis of acquired and intrinsic macrolide phosphotransferases in the Bacillus cereus group.

    PubMed

    Wang, Chao; Sui, Zhihai; Leclercq, Sébastien Olivier; Zhang, Gang; Zhao, Meilin; Chen, Weiqi; Feng, Jie

    2015-05-01

    The Bacillus cereus group is composed of Gram-positive spore-forming bacteria of clinical and ecological importance. More than 200 B. cereus group isolates have been sequenced. However, there are few reports of B. cereus group antibiotic resistance genes. This study identified two functional classes of macrolide phosphotransferases (Mphs) in the B. cereus group. Cluster A Mphs inactivate 14- and 15-membered macrolides while Cluster B Mphs inactivate 14-, 15- and 16-membered compounds. The genomic region surrounding the Cluster B Mph gene is related to various plasmid sequences, suggesting that this gene is an acquired resistance gene. In contrast, the Cluster A Mph gene is located in a chromosomal region conserved among all B. cereus group isolates, and data indicated that it was acquired early in the evolution of the group. Therefore, the Cluster A gene can be considered an intrinsic resistance gene. However, the gene itself is not present in all strains and our comparative genomics analyses showed that it is exchanged among strains of the B. cereus group by the mean of homologous recombination. These results provide an alternative mechanism to intrinsic resistance.

  6. Effects of functional group mass variance on vibrational properties and thermal transport in graphene

    NASA Astrophysics Data System (ADS)

    Lindsay, L.; Kuang, Y.

    2017-03-01

    Intrinsic thermal resistivity critically depends on features of phonon dispersions dictated by harmonic interatomic forces and masses. Here we present the effects of functional group mass variance on vibrational properties and thermal conductivity (κ ) of functionalized graphene from first-principles calculations. We use graphane, a buckled graphene backbone with covalently bonded hydrogen atoms on both sides, as the base material and vary the mass of the hydrogen atoms to simulate the effect of mass variance from other functional groups. We find nonmonotonic behavior of κ with increasing mass of the functional group and an unusual crossover from acoustic-dominated to optic-dominated thermal transport behavior. We connect this crossover to changes in the phonon dispersion with varying mass which suppress acoustic phonon velocities, but also give unusually high velocity optic modes. Further, we show that out-of-plane acoustic vibrations contribute significantly more to thermal transport than in-plane acoustic modes despite breaking of a reflection-symmetry-based scattering selection rule responsible for their large contributions in graphene. This work demonstrates the potential for manipulation and engineering of thermal transport properties in two-dimensional materials toward targeted applications.

  7. Nanomechanical characterization of chemical interaction between gold nanoparticles and chemical functional groups.

    PubMed

    Lee, Gyudo; Lee, Hyungbeen; Nam, Kihwan; Han, Jae-Hee; Yang, Jaemoon; Lee, Sang Woo; Yoon, Dae Sung; Eom, Kilho; Kwon, Taeyun

    2012-10-31

    We report on how to quantify the binding affinity between a nanoparticle and chemical functional group using various experimental methods such as cantilever assay, PeakForce quantitative nanomechanical property mapping, and lateral force microscopy. For the immobilization of Au nanoparticles (AuNPs) onto a microscale silicon substrate, we have considered two different chemical functional molecules of amine and catecholamine (here, dopamine was used). It is found that catecholamine-modified surface is more effective for the functionalization of AuNPs onto the surface than the amine-modified surface, which has been shown from our various experiments. The dimensionless parameter (i.e., ratio of binding affinity) introduced in this work from such experiments is useful in quantitatively depicting such binding affinity, indicating that the binding affinity and stability between AuNPs and catecholamine is approximately 1.5 times stronger than that between amine and AuNPs. Our study sheds light on the experiment-based quantitative characterization of the binding affinity between nanomaterial and chemical groups, which will eventually provide an insight into how to effectively design the functional material using chemical groups.

  8. Nanomechanical characterization of chemical interaction between gold nanoparticles and chemical functional groups

    PubMed Central

    2012-01-01

    We report on how to quantify the binding affinity between a nanoparticle and chemical functional group using various experimental methods such as cantilever assay, PeakForce quantitative nanomechanical property mapping, and lateral force microscopy. For the immobilization of Au nanoparticles (AuNPs) onto a microscale silicon substrate, we have considered two different chemical functional molecules of amine and catecholamine (here, dopamine was used). It is found that catecholamine-modified surface is more effective for the functionalization of AuNPs onto the surface than the amine-modified surface, which has been shown from our various experiments. The dimensionless parameter (i.e., ratio of binding affinity) introduced in this work from such experiments is useful in quantitatively depicting such binding affinity, indicating that the binding affinity and stability between AuNPs and catecholamine is approximately 1.5 times stronger than that between amine and AuNPs. Our study sheds light on the experiment-based quantitative characterization of the binding affinity between nanomaterial and chemical groups, which will eventually provide an insight into how to effectively design the functional material using chemical groups. PMID:23113991

  9. Effects of functional group mass variance on vibrational properties and thermal transport in graphene

    DOE PAGES

    Lindsay, L.; Kuang, Y.

    2017-03-13

    Intrinsic thermal resistivity critically depends on features of phonon dispersions dictated by harmonic interatomic forces and masses. We present the effects of functional group mass variance on vibrational properties and thermal conductivity (κ ) of functionalized graphene from first principles calculations. We also use graphane, a buckled graphene backbone with covalently bonded Hydrogen atoms on both sides, as the base material and vary the mass of the Hydrogen atoms to simulate the effect of mass variance from other functional groups. We find non-monotonic behavior of κ with increasing mass of the functional group and an unusual cross-over from acoustic-dominated tomore » optic-dominated thermal transport behavior. We connect this cross-over to changes in the phonon dispersion with varying mass which suppress acoustic phonon velocities, but also give unusually high velocity optic modes. Further, we show that out-of-plane acoustic vibrations contribute significantly more to thermal transport than in-plane acoustic modes despite breaking of a reflection symmetry based scattering selection rule responsible for their large contributions in graphene. Our work demonstrates the potential for manipulation and engineering of thermal transport properties in two dimensional materials toward targeted applications.« less

  10. Wetland macroinvertebrates of Prentiss Bay, Lake Huron, Michigan: diversity and functional group composition

    USGS Publications Warehouse

    Merritt, R.W.; Benbow, M.E.; Hudson, P.L.

    2002-01-01

    The Great Lakes support many fish and waterbirds that depend directly or indirectly on coastal wetlands during some portion of their life cycle. It is known that macroinvertebrates make up an important part of wetland food webs and ecosystem function; however, our understanding of species distribution within and among wetlands has only recently received attention. We investigated the macroinvertebrates of a freshwater marsh (Prentiss Bay) in the Les Chenaux Island Area of Northern Lake Huron, Michigan. Macroinvertebrate taxa diversity and functional feeding group composition were compared between two habitats. A shallow depositional habitat with higher vegetation diversity and little wave action was compared to a deeper erosional habitat with fewer plant species and more wave action. A total of 83 taxa were collected over the summer of 1996, representing two phyla (Arthropoda and Mollusca) and five classes (Arachnida, Bivalvia, Malacostraca, Gastropoda and Insecta). A total of 79 genera were identified, with 92% being insects (39 families composed of at least 73 genera). Of the total, 42 insect genera were common to both habitats,while relatively fewer were collected exclusively from the erosional compared the depositional habitat. When habitats were pooled, predators comprised about 50% of the functional group taxa, while gathering collectors and shredders each were about 20%. Filtering collectors and scrapers each represented < 10%. When comparing habitats, there was a relatively higher percentage of predators and shredders in the depositional habitat, while all other functional groups were lower. These data suggest that vegetation diversity, depth and wave action affect taxa composition and functional group organization of the Prentiss Bay marsh.

  11. Functionality of In vitro Reconstituted Group II Intron RmInt1-Derived Ribonucleoprotein Particles.

    PubMed

    Molina-Sánchez, Maria D; García-Rodríguez, Fernando M; Toro, Nicolás

    2016-01-01

    The functional unit of mobile group II introns is a ribonucleoprotein particle (RNP) consisting of the intron-encoded protein (IEP) and the excised intron RNA. The IEP has reverse transcriptase activity but also promotes RNA splicing, and the RNA-protein complex triggers site-specific DNA insertion by reverse splicing, in a process called retrohoming. In vitro reconstituted ribonucleoprotein complexes from the Lactococcus lactis group II intron Ll.LtrB, which produce a double strand break, have recently been studied as a means of developing group II intron-based gene targeting methods for higher organisms. The Sinorhizobium meliloti group II intron RmInt1 is an efficient mobile retroelement, the dispersal of which appears to be linked to transient single-stranded DNA during replication. The RmInt1IEP lacks the endonuclease domain (En) and cannot cut the bottom strand to generate the 3' end to initiate reverse transcription. We used an Escherichia coli expression system to produce soluble and active RmInt1 IEP and reconstituted RNPs with purified components in vitro. The RNPs generated were functional and reverse-spliced into a single-stranded DNA target. This work constitutes the starting point for the use of group II introns lacking DNA endonuclease domain-derived RNPs for highly specific gene targeting methods.

  12. Functionality of In vitro Reconstituted Group II Intron RmInt1-Derived Ribonucleoprotein Particles

    PubMed Central

    Molina-Sánchez, Maria D.; García-Rodríguez, Fernando M.; Toro, Nicolás

    2016-01-01

    The functional unit of mobile group II introns is a ribonucleoprotein particle (RNP) consisting of the intron-encoded protein (IEP) and the excised intron RNA. The IEP has reverse transcriptase activity but also promotes RNA splicing, and the RNA-protein complex triggers site-specific DNA insertion by reverse splicing, in a process called retrohoming. In vitro reconstituted ribonucleoprotein complexes from the Lactococcus lactis group II intron Ll.LtrB, which produce a double strand break, have recently been studied as a means of developing group II intron-based gene targeting methods for higher organisms. The Sinorhizobium meliloti group II intron RmInt1 is an efficient mobile retroelement, the dispersal of which appears to be linked to transient single-stranded DNA during replication. The RmInt1IEP lacks the endonuclease domain (En) and cannot cut the bottom strand to generate the 3′ end to initiate reverse transcription. We used an Escherichia coli expression system to produce soluble and active RmInt1 IEP and reconstituted RNPs with purified components in vitro. The RNPs generated were functional and reverse-spliced into a single-stranded DNA target. This work constitutes the starting point for the use of group II introns lacking DNA endonuclease domain-derived RNPs for highly specific gene targeting methods. PMID:27730127

  13. Unification of [FeFe]-hydrogenases into three structural and functional groups

    DOE PAGES

    Poudel, Saroj; Tokmina-Lukaszewska, Monika; Colman, Daniel R.; ...

    2016-05-27

    [FeFe]-hydrogenases (Hyd) are structurally diverse enzymes that catalyze the reversible oxidation of hydrogen (H2). Recent biochemical data demonstrate new functional roles for these enzymes, including those that function in electron bifurcation where an exergonic reaction is coupled with an endergonic reaction to drive the reversible oxidation/production of H2. To identify the structural determinants that underpin differences in enzyme functionality, a total of 714 homologous sequences of the catalytic subunit, HydA, were compiled. Bioinformatics approaches informed by biochemical data were then used to characterize differences in inferred quaternary structure, HydA active site protein environment, accessory iron-sulfur clusters in HydA, and regulatorymore » proteins encoded in HydA gene neighborhoods. HydA homologs were clustered into one of three classification groups, Group 1 (G1), Group 2 (G2), and Group 3 (G3). G1 enzymes were predicted to be monomeric while those in G2 and G3 were predicted to be multimeric and include HydB, HydC (G2/G3) and HydD (G3) subunits. Variation in the HydA active site and accessory iron-sulfur clusters did not vary by group type. Group-specific regulatory genes were identified in the gene neighborhoods of both G2 and G3 Hyd. Analyses of purified G2 and G3 enzymes by mass spectrometry strongly suggests that they are post-translationally modified by phosphorylation. In conclusion, these results suggest that bifurcation capability is dictated primarily by the presence of both HydB and HydC in Hyd complexes, rather than by variation in HydA.« less

  14. Unification of [FeFe]-hydrogenases into three structural and functional groups

    SciTech Connect

    Poudel, Saroj; Tokmina-Lukaszewska, Monika; Colman, Daniel R.; Refai, Mohammed; Schut, Gerrit J.; King, Paul W.; Maness, Pin-Ching; Adams, Michael W. W.; Peters, John W.; Bothner, Brian; Boyd, Eric S.

    2016-05-27

    [FeFe]-hydrogenases (Hyd) are structurally diverse enzymes that catalyze the reversible oxidation of hydrogen (H2). Recent biochemical data demonstrate new functional roles for these enzymes, including those that function in electron bifurcation where an exergonic reaction is coupled with an endergonic reaction to drive the reversible oxidation/production of H2. To identify the structural determinants that underpin differences in enzyme functionality, a total of 714 homologous sequences of the catalytic subunit, HydA, were compiled. Bioinformatics approaches informed by biochemical data were then used to characterize differences in inferred quaternary structure, HydA active site protein environment, accessory iron-sulfur clusters in HydA, and regulatory proteins encoded in HydA gene neighborhoods. HydA homologs were clustered into one of three classification groups, Group 1 (G1), Group 2 (G2), and Group 3 (G3). G1 enzymes were predicted to be monomeric while those in G2 and G3 were predicted to be multimeric and include HydB, HydC (G2/G3) and HydD (G3) subunits. Variation in the HydA active site and accessory iron-sulfur clusters did not vary by group type. Group-specific regulatory genes were identified in the gene neighborhoods of both G2 and G3 Hyd. Analyses of purified G2 and G3 enzymes by mass spectrometry strongly suggests that they are post-translationally modified by phosphorylation. In conclusion, these results suggest that bifurcation capability is dictated primarily by the presence of both HydB and HydC in Hyd complexes, rather than by variation in HydA.

  15. Functional groups in the social behavior of a cichlid fish, the Oscar, Astronotus ocellatus.

    PubMed

    Beeching, S C

    1997-01-01

    Dummy conspecifics were presented to isolated adults of the cichlid fish Astronotus ocellatus to investigate the functional organization of cichlid social behavior. Body size and 15 dummy-elicited activities were recorded during 15 min sessions and analyzed by principal components analysis (PCA) to reveal their temporal organization. Five principal components explained almost 80% of the variation in dummy-elicited behavior, and these five factors define functional groups for Nest-oriented and attack modal action patterns are not mutually inhibitory during this time frame, and biting does not appear to function exclusively during an attack on a conspecific. Comparison with previous studies of New and Old World cichlids suggests evolutionary conservation of the functional organization of social behavior.

  16. Species, Guilds, and Functional Groups: Taxonomy and Behavior in Nematophagous Arthropods

    PubMed Central

    Walter, David Evans; Ikonen, Eeva K.

    1989-01-01

    Phylogenetic relationship is an indication of shared abilities, or at least of shared constraints, on morphology, physiology, and behavior; but is phylogenetic relationship a sufficient criterion for predicting ecological function? Ecologists have assumed that the function of invertebrates in soil systems can be predicted at a low level of taxonomic resolution, but our research indicates that critical functional parameters -- e.g., feeding behavior, developmental rate, and reproductive mode -- are rarely predictable above the generic level. Since morphology is more strongly conserved than behavior, feeding guilds or functional groups based on broad taxonomic relationship or untested assumptions about correlations between trophic morphology and feeding behavior have little meaning for nematophagous arthropods from grassland soils in Colorado. PMID:19287615

  17. Compatibility of functional groups in K[sup ow]-based QSARs: Application to nitro compounds

    SciTech Connect

    Banerjee, S.; Williams, C.L. )

    1993-10-01

    Nitro compounds are particular difficult to handle in simple K[sup ow]-based QSARs, owing to differences in their lipid-phase activity coefficients. These differences can be corrected, in part, through inclusion of a term in octanol solubility. A procedure for identifying potentially incompatible groups in a given QSAR is suggested. The quality of a QSAR is best if the interactions of the functional groups involved with octanol fall within a narrow range. These interactions are easily calculated by the UNIFAC method.

  18. An Application of Functional Renormalization Group Method for Superdense Nuclear Matter

    NASA Astrophysics Data System (ADS)

    Barnaföldi, G. G.; Jakovác, A.; Pósfay, P.

    2017-01-01

    We proposed a method, using the expansion of the effective potential in a base of harmonic functions, to study the Functional Renormalization Group (FRG) method at finite chemical potential. Within this theoretical framework we determined the equation of state and the phase diagram of a simple model of massless fermions coupled to scalars through Yukawa-couling at the zero-temperature limit. Here, we use our FRG-based equation of state to describe the superdense nuclear matter inside compact astrophysical objects. We calculated the mass-radius relation for a compact star using the TOV equation, which was compared to other results.

  19. Universal short-time dynamics: Boundary functional renormalization group for a temperature quench

    NASA Astrophysics Data System (ADS)

    Chiocchetta, Alessio; Gambassi, Andrea; Diehl, Sebastian; Marino, Jamir

    2016-11-01

    We present a method to calculate short-time nonequilibrium universal exponents within the functional-renormalization-group scheme. As an example, we consider the classical critical dynamics of the relaxational model A after a quench of the temperature of the system and calculate the initial-slip exponent which characterizes the nonequilibrium universal short-time behavior of both the order parameter and correlation functions. The value of this exponent is found to be consistent with the result of a perturbative dimensional expansion and of Monte Carlo simulations in three spatial dimensions.

  20. Development and in silico evaluation of large-scale metabolite identification methods using functional group detection for metabolomics

    PubMed Central

    Mitchell, Joshua M.; Fan, Teresa W.-M.; Lane, Andrew N.; Moseley, Hunter N. B.

    2014-01-01

    Large-scale identification of metabolites is key to elucidating and modeling metabolism at the systems level. Advances in metabolomics technologies, particularly ultra-high resolution mass spectrometry (MS) enable comprehensive and rapid analysis of metabolites. However, a significant barrier to meaningful data interpretation is the identification of a wide range of metabolites including unknowns and the determination of their role(s) in various metabolic networks. Chemoselective (CS) probes to tag metabolite functional groups combined with high mass accuracy provide additional structural constraints for metabolite identification and quantification. We have developed a novel algorithm, Chemically Aware Substructure Search (CASS) that efficiently detects functional groups within existing metabolite databases, allowing for combined molecular formula and functional group (from CS tagging) queries to aid in metabolite identification without a priori knowledge. Analysis of the isomeric compounds in both Human Metabolome Database (HMDB) and KEGG Ligand demonstrated a high percentage of isomeric molecular formulae (43 and 28%, respectively), indicating the necessity for techniques such as CS-tagging. Furthermore, these two databases have only moderate overlap in molecular formulae. Thus, it is prudent to use multiple databases in metabolite assignment, since each major metabolite database represents different portions of metabolism within the biosphere. In silico analysis of various CS-tagging strategies under different conditions for adduct formation demonstrate that combined FT-MS derived molecular formulae and CS-tagging can uniquely identify up to 71% of KEGG and 37% of the combined KEGG/HMDB database vs. 41 and 17%, respectively without adduct formation. This difference between database isomer disambiguation highlights the strength of CS-tagging for non-lipid metabolite identification. However, unique identification of complex lipids still needs additional

  1. Development and in silico evaluation of large-scale metabolite identification methods using functional group detection for metabolomics.

    PubMed

    Mitchell, Joshua M; Fan, Teresa W-M; Lane, Andrew N; Moseley, Hunter N B

    2014-01-01

    Large-scale identification of metabolites is key to elucidating and modeling metabolism at the systems level. Advances in metabolomics technologies, particularly ultra-high resolution mass spectrometry (MS) enable comprehensive and rapid analysis of metabolites. However, a significant barrier to meaningful data interpretation is the identification of a wide range of metabolites including unknowns and the determination of their role(s) in various metabolic networks. Chemoselective (CS) probes to tag metabolite functional groups combined with high mass accuracy provide additional structural constraints for metabolite identification and quantification. We have developed a novel algorithm, Chemically Aware Substructure Search (CASS) that efficiently detects functional groups within existing metabolite databases, allowing for combined molecular formula and functional group (from CS tagging) queries to aid in metabolite identification without a priori knowledge. Analysis of the isomeric compounds in both Human Metabolome Database (HMDB) and KEGG Ligand demonstrated a high percentage of isomeric molecular formulae (43 and 28%, respectively), indicating the necessity for techniques such as CS-tagging. Furthermore, these two databases have only moderate overlap in molecular formulae. Thus, it is prudent to use multiple databases in metabolite assignment, since each major metabolite database represents different portions of metabolism within the biosphere. In silico analysis of various CS-tagging strategies under different conditions for adduct formation demonstrate that combined FT-MS derived molecular formulae and CS-tagging can uniquely identify up to 71% of KEGG and 37% of the combined KEGG/HMDB database vs. 41 and 17%, respectively without adduct formation. This difference between database isomer disambiguation highlights the strength of CS-tagging for non-lipid metabolite identification. However, unique identification of complex lipids still needs additional

  2. N-containing functional groups induced superior cytocompatible and hemocompatible graphene by NH₂ ion implantation.

    PubMed

    Guo, Meixian; Li, Minsi; Liu, Xiaoqi; Zhao, Mengli; Li, Dejun; Geng, Dongsheng; Sun, Xueliang; Gu, Hanqing

    2013-12-01

    Graphene is functionalized with amine by NH2 ion implantation at room temperature in vacuum. The reaction is featured by nucleophilic substitution of C-O groups by the ammonia radicals. The presence of N-containing functional groups in graphene is identified by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. N element was successfully introduced to graphene, the atomic ratio of N to C rose to 3.12 %. NH2 ion implanted graphene (G-NH2) is a better hydrophilic material than pristine grahene according to the contact angle experiment. Mouse fibroblast cells and human endothelial cells cultured on G-NH2 displayed superior cell-viability, proliferation and stretching over that on pristine graphene. Platelet adhesion, hemolysis and Kinetic-clotting time were measured on G-NH2, showing excellent anticoagulation, with as good hemolysis as pristine graphene.

  3. Preparation and properties of a novel biodegradable polyester elastomer with functional groups.

    PubMed

    Liu, Quan-Yong; Wu, Si-Zhu; Tan, Tian-Wei; Weng, Jing-Yi; Zhang, Li-Qun; Liu, Li; Tian, Wei; Chen, Da-Fu

    2009-01-01

    A novel biodegradable poly(sebacate-glycerol-citrate) (PGSC) elastomer with functional groups was prepared in this study. First, moldable mixtures were obtained by mixing citric acid with the poly(glycerol-sebacate) (PGS) pre-polymers synthesized in our lab. The PGSC elastomers were obtained from moldable mixtures that were thermally cured in the moulds. Then, the structures, compositions and properties of the elastomers were studied by Fourier transformation infrared spectroscopy (FT-IR), swelling test, differential scanning calorimeter (DSC), tensile test, water contact angle measurement, water absorption experiments and a in vitro degradation test. It showed that the hydroxyl groups remained in the elastomers which would endow the polymer chains with functionality such as good surface modification. By controlling the thermal curing time, the compositions of the PGSC elastomers were adjusted for different mechanical and biodegradable properties. Therefore, PGSC elastomers might be used as anti-conglutination films in surgery, guided tissue regeneration membranes and drug-delivery matrices.

  4. Approaching many-body localization from disordered Luttinger liquids via the functional renormalization group

    NASA Astrophysics Data System (ADS)

    Karrasch, C.; Moore, J. E.

    2015-09-01

    We study the interplay of interactions and disorder in a one-dimensional fermion lattice coupled adiabatically to infinite reservoirs. We employ both the functional renormalization group (FRG) as well as matrix product state techniques, which serve as an accurate benchmark for small systems. Using the FRG, we compute the length- and temperature-dependence of the conductance averaged over 104 samples for lattices as large as 105 sites. We identify regimes in which non-Ohmic power law behavior can be observed and demonstrate that the corresponding exponents can be understood by adapting earlier predictions obtained perturbatively for disordered Luttinger liquids. In the presence of both disorder and isolated impurities, the conductance has a universal single-parameter scaling form. This lays the groundwork for an application of the functional renormalization group to the realm of many-body localization.

  5. How surface functional groups influence fracturation in nanofluids droplets dry-outs

    NASA Astrophysics Data System (ADS)

    Brutin, David; Carle, Florian

    2012-11-01

    We report an experimental investigation of the drying of a deposited droplets of nanofluids with different surface functional groups. For identical nano-particles diameter, material and concentration, identical drying conditions, the substrate and the functional groups at the nano-particles surface are changed. Both flow motion, adhesion, gelation and fracturation occur during the evaporation of this complex matter leading to different final typical patterns. The differences in between the patterns are explained based on the surface chemical potential. Crack shapes and wavelengths are globally proportional to the electrical charges carried at the nano- particles surface which is a new parameter to implement in existing predicting models. Presently only the colloid concentration and softness and the deposit thickness are used (Allain and Limat, 1995). The authors gratefully acknowledge the help and the fruitful discussions raised with J.B. Lang.

  6. Assemblage patterns of fish functional groups relative to habitat connectivity and conditions in floodplain lakes

    USGS Publications Warehouse

    Miyazono, S.; Aycock, J.N.; Miranda, L.E.; Tietjen, T.E.

    2010-01-01

    We evaluated the influences of habitat connectivity and local environmental factors on the distribution and abundance patterns of fish functional groups in 17 floodplain lakes in the Yazoo River Basin, USA. The results of univariate and multivariate analyses showed that species-environmental relationships varied with the functional groups. Species richness and assemblage structure of periodic strategists showed strong and positive correlations with habitat connectivity. Densities of most equilibrium and opportunistic strategists decreased with habitat connectivity. Densities of certain equilibrium and opportunistic strategists increased with turbidity. Forested wetlands around the lakes were positively related to the densities of periodic and equilibrium strategists. These results suggest that decreases in habitat connectivity, forested wetland buffers and water quality resulting from environmental manipulations may cause local extinction of certain fish taxa and accelerate the dominance of tolerant fishes in floodplain lakes. ?? 2010 John Wiley & Sons A/S.

  7. The Donaldson-Witten Function for Gauge Groups of Rank Larger Than One

    NASA Astrophysics Data System (ADS)

    Mariño, Marcos; Moore, Gregory

    We study correlation functions in topologically twisted , d=4 supersymmetric Yang-Mills theory for gauge groups of rank larger than one on compact four-manifolds X. We find that the topological invariance of the generator of correlation functions of BRST invariant observables is not spoiled by noncompactness of field space. We show how to express the correlators on simply connected manifolds of b2,+(X)>0 in terms of Seiberg-Witten invariants and the classical cohomology ring of X. For manifolds X of simple type and gauge group SU(N) we give explicit expressions of the correlators as a sum over =1 vacua. We describe two applications of our expressions, one to superconformal field theory and one to large N expansions of SU(N) , d=4 supersymmetric Yang-Mills theory.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  9. Theoretical elucidation on the functional role of pyrrolidine-type ionic liquids in inducing stereoselectivity of the Michael addition of cyclohexanone with trans-β-nitrostyrene.

    PubMed

    Sun, Hui; Zhang, Dongju

    2011-03-01

    Density functional theory calculations have been carried out to elucidate the stereoselectivity of the Michael addition of cyclohexanone with trans-β-nitrostyrene, induced by a chiral ionic liquid (CIL) pyrrolidine-imidazolium bromide. By comparison of the C-C bond forming processes in the absence and presence of Br(-) anion, we found that intermolecular H-bonds between the imidazolium cation and the nitro group of trans-β-nitrostyrene and the steric hindrance of the imidazolium cation moiety on the Si-face of enamine dominate the stereoselectivity of the Michael addition. The presence of Br(-) anion obviously reduces the barrier by increasing the polarity of the C4=C5 bond of enamine. The theoretical results rationalize well the early experimental finding, and reveal a valuable clue for the further CIL design with high catalytic efficiency.

  10. Preconversion catalytic deoxygenation of phenolic functional groups. Quarterly report, January 1--March 30, 1996

    SciTech Connect

    Kubiak, C.P.

    1996-12-31

    Over the course of the studies on catalytic deoxygenation of phenolic residues in coal by carbon monoxide, the author performed preliminary investigations into the removal of other heteroatom groups. This report describes the attempted carbonylation of phenyl amido complexes. These studies resulted in the surprisingly facile formation of amidines. The amidine group is the nitrogen analog of carboxylic acids and esters. This functional group combines the properties of an azomethane-like C=N double bond with an amide-like C-N single bond. This group, like the related allyl (C-C-C), aza-allyl (C-N-C), and carboxylato (O-C-O) groups, form a number of transition metal derivatives, with both early and late transition metals. Various bonding modes of the amidino group have been reported. However, most isolated complexes have the amidino ligand as a chelating ligand or bridging two metals. This is due to the preference of amidines to bond via the nitrogen lone pairs, in contrast to the {eta}3 bonding observed in metal-allyl complexes. The experimental section of the paper describes the synthesis of platinum complexes, X-ray diffraction data for one Pt complex, and its reaction with carbon monoxide. Results are presented on the crystal and molecular structure of a platinum complex.

  11. Quantitative Evaluation of the Dispersion of Graphene Sheets With and Without Functional Groups Using Molecular Dynamics Simulations

    NASA Astrophysics Data System (ADS)

    Cha, JinHyeok; Kyoung, Woomin; Song, Kyonghwa; Park, Sangbaek; Lim, Taewon; Lee, Jongkook; Kang, Hyunmin

    2016-03-01

    Nanofluids with enhanced thermal properties are candidates for thermal management in automotive systems, with scope for improving energy efficiency. In particular, many studies have reported on dispersions of nanoparticles with long-term stability in the base fluid, with qualitative evaluations of the dispersion stability via either the naked eye or optical instruments. Additives such as surfactants can be used to enhance the dispersion of nanoparticles; however, this may diminish their intrinsic thermal properties. Here, we describe molecular dynamics simulations of nanofluids containing graphene sheets dispersed in ethylene glycol and water. We go on to suggest a quantitative evaluation method for the degree of dispersion, based on the ratio of the total number of nanoparticles to the number of clustered nanoparticles. Moreover, we investigate the effects of functional groups on the surface of graphene, which are expected to improve the dispersion without requiring additives such as surfactants due to steric hindrance and chemical affinity for the surrounding fluid. We find that, for pure graphene, the degree of dispersion decreased as the quantity of graphene sheets increased, which is attributed to an increased probability of aggregation at higher loadings; however, the presence of functional groups inhibited the graphene sheets from forming aggregates.

  12. Quantitative Evaluation of the Dispersion of Graphene Sheets With and Without Functional Groups Using Molecular Dynamics Simulations.

    PubMed

    Cha, JinHyeok; Kyoung, Woomin; Song, Kyonghwa; Park, Sangbaek; Lim, Taewon; Lee, Jongkook; Kang, Hyunmin

    2016-12-01

    Nanofluids with enhanced thermal properties are candidates for thermal management in automotive systems, with scope for improving energy efficiency. In particular, many studies have reported on dispersions of nanoparticles with long-term stability in the base fluid, with qualitative evaluations of the dispersion stability via either the naked eye or optical instruments. Additives such as surfactants can be used to enhance the dispersion of nanoparticles; however, this may diminish their intrinsic thermal properties. Here, we describe molecular dynamics simulations of nanofluids containing graphene sheets dispersed in ethylene glycol and water. We go on to suggest a quantitative evaluation method for the degree of dispersion, based on the ratio of the total number of nanoparticles to the number of clustered nanoparticles. Moreover, we investigate the effects of functional groups on the surface of graphene, which are expected to improve the dispersion without requiring additives such as surfactants due to steric hindrance and chemical affinity for the surrounding fluid. We find that, for pure graphene, the degree of dispersion decreased as the quantity of graphene sheets increased, which is attributed to an increased probability of aggregation at higher loadings; however, the presence of functional groups inhibited the graphene sheets from forming aggregates.

  13. Temporal lobe contribution to perceptual function: A tale of three patient groups.

    PubMed

    Behrmann, M; Lee, A C H; Geskin, J Z; Graham, K S; Barense, M D

    2016-09-01

    There has been growing recognition of the contribution of medial and anterior temporal lobe structures to non-mnemonic functions, such as perception. To evaluate the nature of this contribution, we contrast the perceptual performance of three patient groups, all of whom have a perturbation of these temporal lobe structures. Specifically, we compare the profile of patients with focal hippocampal (HC) lesions, those with more extensive lesions to the medial temporal lobe (MTL) that include HC and perirhinal cortex (PrC), and those with congenital prosopagnosia (CP), whose deficit has been attributed to the disconnection of the anterior temporal lobe from more posterior structures. All participants completed a range of'oddity' tasks in which, on each trial, they determined which of four visual stimuli in a display was the'odd-one-out'. There were five stimulus categories including faces, scenes, objects (high and low ambiguity) and squares of different sizes. Comparisons were conducted separately for the HC, MTL and CP groups against their matched control groups and then the group data were compared to each other directly. The group profiles were easily differentiable. Whereas the HC group stood out for its difficulty in discriminating scenes and the CP group stood out for its disproportionate difficulty in discriminating faces with milder effects for scenes and high ambiguity objects, the MTL group evinced a more general discrimination deficit for faces, scenes and high ambiguity objects. The group differences highlight distinct profiles for each of the three groups and distinguish the signature perceptual impairments following more extended temporal lobe alterations. In the recent reconsideration of the role of the hippocampus and neocortex, Moscovitch and colleagues (Moscovitch et al., 2016) note that the medial temporal lobe structures play a role in non-mnemonic functions, such as perception, problem solving, decision-making and language. Here, we address this

  14. β-Diversity of functional groups of woody plants in a tropical dry forest in Yucatan.

    PubMed

    López-Martínez, Jorge Omar; Sanaphre-Villanueva, Lucía; Dupuy, Juan Manuel; Hernández-Stefanoni, José Luis; Meave, Jorge Arturo; Gallardo-Cruz, José Alberto

    2013-01-01

    Two main theories have attempted to explain variation in plant species composition (β-diversity). Niche theory proposes that most of the variation is related to environment (environmental filtering), whereas neutral theory posits that dispersal limitation is the main driver of β-diversity. In this study, we first explored how α- and β-diversity of plant functional groups defined by growth form (trees, shrubs and lianas, which represent different strategies of resource partitioning), and dispersal syndrome (autochory, anemochory and zoochory, which represent differences in dispersal limitation) vary with successional age and topographic position in a tropical dry forest. Second, we examined the effects of environmental, spatial, and spatially-structured environmental factors on β-diversity of functional groups; we used the spatial structure of sampling sites as a proxy for dispersal limitation, and elevation, soil properties and forest stand age as indicators of environmental filtering. We recorded 200 species and 22,245 individuals in 276 plots; 120 species were trees, 41 shrubs and 39 lianas. We found that β-diversity was highest for shrubs, intermediate for lianas and lowest for trees, and was slightly higher for zoochorous than for autochorous and anemochorous species. All three dispersal syndromes, trees and shrubs varied in composition among vegetation classes (successional age and topographic position), whilst lianas did not. β-diversity was influenced mostly by proxies of environmental filtering, except for shrubs, for which the influence of dispersal limitation was more important. Stand age and topography significantly influenced α-diversity across functional groups, but showed a low influence on β-diversity -possibly due to the counterbalancing effect of resprouting on plant distribution and composition. Our results show that considering different plant functional groups reveals important differences in both α- and β-diversity patterns and

  15. β-Diversity of Functional Groups of Woody Plants in a Tropical Dry Forest in Yucatan

    PubMed Central

    López-Martínez, Jorge Omar; Sanaphre-Villanueva, Lucía; Dupuy, Juan Manuel; Hernández-Stefanoni, José Luis; Meave, Jorge Arturo; Gallardo-Cruz, José Alberto

    2013-01-01

    Two main theories have attempted to explain variation in plant species composition (β-diversity). Niche theory proposes that most of the variation is related to environment (environmental filtering), whereas neutral theory posits that dispersal limitation is the main driver of β-diversity. In this study, we first explored how α- and β-diversity of plant functional groups defined by growth form (trees, shrubs and lianas, which represent different strategies of resource partitioning), and dispersal syndrome (autochory, anemochory and zoochory, which represent differences in dispersal limitation) vary with successional age and topographic position in a tropical dry forest. Second, we examined the effects of environmental, spatial, and spatially-structured environmental factors on β-diversity of functional groups; we used the spatial structure of sampling sites as a proxy for dispersal limitation, and elevation, soil properties and forest stand age as indicators of environmental filtering. We recorded 200 species and 22,245 individuals in 276 plots; 120 species were trees, 41 shrubs and 39 lianas. We found that β-diversity was highest for shrubs, intermediate for lianas and lowest for trees, and was slightly higher for zoochorous than for autochorous and anemochorous species. All three dispersal syndromes, trees and shrubs varied in composition among vegetation classes (successional age and topographic position), whilst lianas did not. β-diversity was influenced mostly by proxies of environmental filtering, except for shrubs, for which the influence of dispersal limitation was more important. Stand age and topography significantly influenced α-diversity across functional groups, but showed a low influence on β-diversity –possibly due to the counterbalancing effect of resprouting on plant distribution and composition. Our results show that considering different plant functional groups reveals important differences in both α- and β-diversity patterns and

  16. Harmonic expansion of the effective potential in a functional renormalization group at finite chemical potential

    NASA Astrophysics Data System (ADS)

    Barnaföldi, G. G.; Jakovác, A.; Pósfay, P.

    2017-01-01

    In this paper we propose a method to study the functional renormalization group (FRG) at finite chemical potential. The method consists of mapping the FRG equations within the Fermi surface into a differential equation defined on a rectangle with zero boundary conditions. To solve this equation we use an expansion of the potential in a harmonic basis. With this method we determined the phase diagram of a simple Yukawa-type model; as expected, the bosonic fluctuations decrease the strength of the transition.

  17. Isgur-Wise functions and unitary representations of the Lorentz group: The baryon case j=0

    SciTech Connect

    Le Yaouanc, A.; Oliver, L.; Raynal, J.-C.

    2009-09-01

    We propose a group theoretical method to study Isgur-Wise (IW) functions. A current matrix element splits into a heavy quark matrix element and an overlap of the initial and final clouds, related to the IW functions, that contain the long distance physics. The light cloud belongs to the Hilbert space of a unitary representation of the Lorentz group. Decomposing into irreducible representations one obtains the IW function as an integral formula, superposition of irreducible IW functions with positive measures, providing positivity bounds on its derivatives. Our method is equivalent to the sum rule approach, but sheds another light on the physics and summarizes and gives all its possible constraints. We expose the general formalism, thoroughly applying it to the case j=0 for the light cloud, relevant to the semileptonic decay {lambda}{sub b}{yields}{lambda}{sub c}l{nu}{sub l}. In this case, the principal series of the representations contribute, and also the supplementary series. We recover the bound for the curvature of the j=0 IW function {xi}{sub {lambda}}(w) that we did obtain from the sum rule method, and we get new bounds for higher derivatives. We demonstrate also that if the lower bound for the curvature is saturated, then {xi}{sub {lambda}}(w) is completely determined, given by an explicit elementary function. We give criteria to decide if any Ansatz for the Isgur-Wise function is compatible or not with the sum rules. We apply the method to some simple model forms proposed in the literature. Dealing with a Hilbert space, the sum rules are convergent, but this feature does not survive hard gluon radiative corrections.

  18. Biodegradable polyglycerols with randomly distributed ketal groups as multi-functional drug delivery systems.

    PubMed

    Shenoi, Rajesh A; Lai, Benjamin F L; Imran ul-haq, Muhammad; Brooks, Donald E; Kizhakkedathu, Jayachandran N

    2013-08-01

    Biodegradable multi-functional polymeric nanostructures that undergo controlled degradation in response to physiological cues are important in numerous biomedical applications including drug delivery, bio-conjugation and tissue engineering. In this paper, we report the development of a new class of water soluble multi-functional branched biodegradable polymer with high molecular weight and biocompatibility which demonstrates good correlation of in vivo biodegradation and in vitro hydrolysis. Main chain degradable hyperbranched polyglycerols (HPG) (20-100 kDa) were synthesized by the introduction of acid labile groups within the polymer structure by an anionic ring opening copolymerization of glycidol with ketal-containing epoxide monomers with different ketal structures. The water soluble biodegradable HPGs with randomly distributed ketal groups (RBHPGs) showed controlled degradation profiles in vitro depending on the pH of solution, temperature and the structure of incorporated ketal groups, and resulted in non-toxic degradation products. NMR studies demonstrated the branched nature of RBHPGs which is correlating with their smaller hydrodynamic radii. The RBHPGs and their degradation products exhibited excellent blood compatibility and tissue compatibility based on various analyses methods, independent of their molecular weight and ketal group structure. When administered intravenously in mice, tritium labeled RBHPG of molecular weight 100 kDa with dimethyl ketal group showed a circulation half life of 2.7 ± 0.3 h, correlating well with the in vitro polymer degradation half life (4.3 h) and changes in the molecular weight profile during the degradation (as measured by gel permeation chromatography) in buffer conditions at 37 °C. The RBHPG degraded into low molecular weight fragments that were cleared from circulation rapidly. The biodistribution and excretion studies demonstrated that RBHPG exhibited significantly lower tissue accumulation and enhanced urinary

  19. Small functional groups for controlled differentiation of hydrogel-encapsulated human mesenchymal stem cells

    NASA Astrophysics Data System (ADS)

    Benoit, Danielle S. W.; Schwartz, Michael P.; Durney, Andrew R.; Anseth, Kristi S.

    2008-10-01

    Cell-matrix interactions have critical roles in regeneration, development and disease. The work presented here demonstrates that encapsulated human mesenchymal stem cells (hMSCs) can be induced to differentiate down osteogenic and adipogenic pathways by controlling their three-dimensional environment using tethered small-molecule chemical functional groups. Hydrogels were formed using sufficiently low concentrations of tether molecules to maintain constant physical characteristics, encapsulation of hMSCs in three dimensions prevented changes in cell morphology, and hMSCs were shown to differentiate in normal growth media, indicating that the small-molecule functional groups induced differentiation. To our knowledge, this is the first example where synthetic matrices are shown to control induction of multiple hMSC lineages purely through interactions with small-molecule chemical functional groups tethered to the hydrogel material. Strategies using simple chemistry to control complex biological processes would be particularly powerful as they could make production of therapeutic materials simpler, cheaper and more easily controlled.

  20. Surface modification influencing adsorption of red wine constituents: The role of functional groups

    NASA Astrophysics Data System (ADS)

    Mierczynska-Vasilev, Agnieszka; Smith, Paul A.

    2016-11-01

    The adsorption of wine constituents at solid surfaces is important in applications such as filtration and membrane fouling, binding to tanks and fittings and interactions with processing aids such as bentonite. The interaction of wine constituents with surfaces is mediated through adsorbed wine components, where the type of constituents, amount, orientation, and conformation are of consequence for the surface response. This study examines the effect of surface chemical functionalities on the adsorption of red wine constituents. Plasma-polymerized films rich in amine, carboxyl, hydroxyl, formyl and methyl functional groups were generated on solid substrates whereas, glycidyltrimethylammonium chloride was covalently attached to allylamine plasma-polymer modified surface and poly(sodium styrenesulfonate) was electrostatically adsorbed to an amine plasma-polymerized surface. The surface chemical functionalities were characterized by X-ray photoelectron spectroscopy. The ability of different substrates to adsorb red wine constituents was evaluated by quartz crystal microbalance and atomic force microscopy. The results showed that substrates modified with -SO3H and -COOH groups can adsorb more of the wine nitrogen-containing compounds whereas -NH2 and -NR3 groups encourage carbon-containing compounds adsorption. Red wine constituents after filtration were adsorbed in higher extend on -NR3 and -CHO surfaces. The -OH modified surfaces had the lowest ability to absorb wine components.

  1. Prediction of cloud condensation nuclei activity for organic compounds using functional group contribution methods

    DOE PAGES

    Petters, M. D.; Kreidenweis, S. M.; Ziemann, P. J.

    2016-01-19

    A wealth of recent laboratory and field experiments demonstrate that organic aerosol composition evolves with time in the atmosphere, leading to changes in the influence of the organic fraction to cloud condensation nuclei (CCN) spectra. There is a need for tools that can realistically represent the evolution of CCN activity to better predict indirect effects of organic aerosol on clouds and climate. This work describes a model to predict the CCN activity of organic compounds from functional group composition. Following previous methods in the literature, we test the ability of semi-empirical group contribution methods in Köhler theory to predict themore » effective hygroscopicity parameter, kappa. However, in our approach we also account for liquid–liquid phase boundaries to simulate phase-limited activation behavior. Model evaluation against a selected database of published laboratory measurements demonstrates that kappa can be predicted within a factor of 2. Simulation of homologous series is used to identify the relative effectiveness of different functional groups in increasing the CCN activity of weakly functionalized organic compounds. Hydroxyl, carboxyl, aldehyde, hydroperoxide, carbonyl, and ether moieties promote CCN activity while methylene and nitrate moieties inhibit CCN activity. The model can be incorporated into scale-bridging test beds such as the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to evaluate the evolution of kappa for a complex mix of organic compounds and to develop suitable parameterizations of CCN evolution for larger-scale models.« less

  2. Prediction of cloud condensation nuclei activity for organic compounds using functional group contribution methods

    NASA Astrophysics Data System (ADS)

    Petters, M. D.; Kreidenweis, S. M.; Ziemann, P. J.

    2016-01-01

    A wealth of recent laboratory and field experiments demonstrate that organic aerosol composition evolves with time in the atmosphere, leading to changes in the influence of the organic fraction to cloud condensation nuclei (CCN) spectra. There is a need for tools that can realistically represent the evolution of CCN activity to better predict indirect effects of organic aerosol on clouds and climate. This work describes a model to predict the CCN activity of organic compounds from functional group composition. Following previous methods in the literature, we test the ability of semi-empirical group contribution methods in Köhler theory to predict the effective hygroscopicity parameter, kappa. However, in our approach we also account for liquid-liquid phase boundaries to simulate phase-limited activation behavior. Model evaluation against a selected database of published laboratory measurements demonstrates that kappa can be predicted within a factor of 2. Simulation of homologous series is used to identify the relative effectiveness of different functional groups in increasing the CCN activity of weakly functionalized organic compounds. Hydroxyl, carboxyl, aldehyde, hydroperoxide, carbonyl, and ether moieties promote CCN activity while methylene and nitrate moieties inhibit CCN activity. The model can be incorporated into scale-bridging test beds such as the Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to evaluate the evolution of kappa for a complex mix of organic compounds and to develop suitable parameterizations of CCN evolution for larger-scale models.

  3. Chemical functionalization of nanodiamond by amino groups: an X-ray photoelectron spectroscopy study.

    PubMed

    Dhanak, V R; Butenko, Yu V; Brieva, A C; Coxon, P R; Alves, L; Siller, L

    2012-04-01

    The development of chemical functionalization techniques for diamond nanocrystallites opens up ways with a view to altering their solubility in different solvents, improve interfacial adhesion of nanodiamonds with a composite matrix in new materials, and provide new possibilities for the modification of the electronic properties of nanodiamond crystallites. In this work, we present results on the chemical functionalization of nanodiamonds by amino groups using ammonia as a nitrogenation agent. Nanodiamond material used was formed by the detonation technique with average crystallite sizes of 4-5 nm. The final materials and intermediates products were characterized by Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Chemical functionalization of nanodiamonds by amino groups could enable the preparation of new nylon nano-composite materials. Presence of surface amino groups could alter pH of nanodiamond colloids towards basic values and improve colloidal stability of nanodiamond suspensions at pH close to 7. This could enable syntheses of new drug delivery systems based on nanodiamonds.

  4. A guide to the selection of switchable functional groups for CO2-switchable compounds.

    PubMed

    Alshamrani, A K; Vanderveen, J R; Jessop, P G

    2016-07-28

    Many CO2-responsive species, including many of the CO2-switchable surfactants, solvents, solutes, gels, colloids, and surfaces, rely on the ability of CO2 to lower the pH of water. Uncharged basic groups on the CO2-responsive species are therefore converted from a neutral state to a protonated cationic state (a bicarbonate salt), which causes dramatic and useful changes to the properties of the species. However, this switching process only works correctly if a basic group of appropriate basicity has been selected. This article presents a comprehensive guide to the selection of basic groups for CO2-switchable species for use in water. The appropriate basicity, as measured by the pKaH (the pKa of the protonated compound), is a function of the concentration of the switchable species, the temperature, the pressure of CO2, the presence or absence of an organic liquid phase, and the solubility of the neutral form of the compound.

  5. Magneto-Sensitive Adsorbents Modified by Functional Nitrogen-Containing Groups

    NASA Astrophysics Data System (ADS)

    Melnyk, Inna V.; Gdula, Karolina; Dąbrowski, Andrzej; Zub, Yuriy L.

    2016-02-01

    In order to obtain amino-functionalized silica materials with magnetic core, one-step synthesis was carried out. Several materials, differ in number and structure of amino groups, were synthesized on the basis of sol-gel method. The synthesized materials were examined by several analytical techniques. The presence and content of amino groups were measured by using Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy and acid-base titration, respectively. Specific surface areas were measured by nitrogen/adsorption desorption isotherms. It was proved that sol-gel approach leads to obtain materials with high content of amino groups built into their surfaces (in the range 1.6-2.7 mmol/g). As-obtained materials were tested as potential adsorbents for copper(II) ions. The received maximum adsorption capacities were in the range 0.4-0.7 mmol/g.

  6. Identifying functional groups for response to disturbance in an abandoned pasture

    NASA Astrophysics Data System (ADS)

    Lavorel, Sandra; Touzard, Blaise; Lebreton, Jean-Dominique; Clément, Bernard

    1998-06-01

    In an abandoned pasture in Brittany, we compared artificial small-scale disturbances to natural disturbances by wild boar and undisturbed vegetation. We developed a multivariate statistical approach which analyses how species biological attributes explain the response of community composition to disturbances. This technique, which reconciles the inductive and deductive approaches for functional classifications, identifies groups of species with similar responses to disturbance and characterizes their biological profiles. After 5 months of recolonization, artificial disturbances had a greater species richness than undisturbed vegetation as a result of recruitment of new species without the exclusion of pre-existing matrix species. Species morphology, described by canopy structure, canopy height and lateral spread, explained a large part (16 %) of community response to disturbance. Regeneration strategies, described by life history, seed mass, dispersal agent, dormancy and the existence of vegetative multiplication, explained a smaller part of community response to disturbance (8 %). Artificial disturbances were characterized by therophyte and compact rosettes with moderately dormant seeds, including a number of Asteraceae and other early successional species. Natural disturbances were colonized by leafy guerrilla species without seed dormancy. Few species were tightly related to undisturbed vegetation and were essentially grasses with a phalanx rosette morphology. The functional classification obtained is consistent with the classification of the community into fugitives, regenerators and persistors. These groups are structured according to Grubb's model for temperate grasslands, with regenerators and persistors in the matrix and fugitives taking advantage of gaps open by small-scale disturbances. The conjunction of functional diversity and species diversity within functional groups is the key to resilience to disturbance, an important ecosystem function.

  7. The two-point correlation function for groups of galaxies in the Center for Astrophysics redshift survey

    NASA Technical Reports Server (NTRS)

    Ramella, Massimo; Geller, Margaret J.; Huchra, John P.

    1990-01-01

    The large-scale distribution of groups of galaxies selected from complete slices of the CfA redshift survey extension is examined. The survey is used to reexamine the contribution of group members to the galaxy correlation function. The relationship between the correlation function for groups and those calculated for rich clusters is discussed, and the results for groups are examined as an extension of the relation between correlation function amplitude and richness. The group correlation function indicates that groups and individual galaxies are equivalent tracers of the large-scale matter distribution. The distribution of group centers is equivalent to random sampling of the galaxy distribution. The amplitude of the correlation function for groups is consistent with an extrapolation of the amplitude-richness relation for clusters. The amplitude scaled by the mean intersystem separation is also consistent with results for richer clusters.

  8. Different Effect of the Additional Electron-Withdrawing Cyano Group in Different Conjugation Bridge: The Adjusted Molecular Energy Levels and Largely Improved Photovoltaic Performance.

    PubMed

    Li, Huiyang; Fang, Manman; Hou, Yingqin; Tang, Runli; Yang, Yizhou; Zhong, Cheng; Li, Qianqian; Li, Zhen

    2016-05-18

    Four organic sensitizers (LI-68-LI-71) bearing various conjugated bridges were designed and synthesized, in which the only difference between LI-68 and LI-69 (or LI-70 and LI-71) was the absence/presence of the CN group as the auxiliary electron acceptor. Interestingly, compared to the reference dye of LI-68, LI-69 bearing the additional CN group exhibited the bad performance with the decreased Jsc and Voc values. However, once one thiophene moiety near the anchor group was replaced by pyrrole with the electron-rich property, the resultant LI-71 exhibited a photoelectric conversion efficiency increase by about 3 folds from 2.75% (LI-69) to 7.95% (LI-71), displaying the synergistic effect of the two moieties (CN and pyrrole). Computational analysis disclosed that pyrrole as the auxiliary electron donor (D') in the conjugated bridge can compensate for the lower negative charge in the electron acceptor, which was caused by the CN group as the electron trap, leading to the more efficient electron injection and better photovoltaic performance.

  9. Living Additive Manufacturing: Transformation of Parent Gels into Diversely Functionalized Daughter Gels Made Possible by Visible Light Photoredox Catalysis.

    PubMed

    Chen, Mao; Gu, Yuwei; Singh, Awaneesh; Zhong, Mingjiang; Jordan, Alex M; Biswas, Santidan; Korley, LaShanda T J; Balazs, Anna C; Johnson, Jeremiah A

    2017-02-22

    Light-initiated additive manufacturing techniques typically rely on layer-by-layer addition or continuous extraction of polymers formed via nonliving, free radical polymerization methods that render the final materials "dead" toward further monomer insertion; the polymer chains within the materials cannot be reactivated to induce chain extension. An alternative "living additive manufacturing" strategy would involve the use of photocontrolled living radical polymerization to spatiotemporally insert monomers into dormant "parent" materials to generate more complex and diversely functionalized "daughter" materials. Here, we demonstrate a proof-of-concept study of living additive manufacturing using end-linked polymer gels embedded with trithiocarbonate iniferters that can be activated by photoinduced single-electron transfer from an organic photoredox catalyst in solution. This system enables the synthesis of a wide range of chemically and mechanically differentiated daughter gels from a single type of parent gel via light-controlled modification of the parent's average composition, strand length, and/or cross-linking density. Daughter gels that are softer than their parent, stiffer than their parent, larger but with the same modulus as their parent, thermally responsive, polarity responsive, healable, and weldable are all realized.

  10. Additives enhancing the catalytic properties of lipase from Burkholderia cepacia immobilized on mixed-function-grafted mesoporous silica gel.

    PubMed

    Abaházi, Emese; Boros, Zoltán; Poppe, László

    2014-07-08

    Effects of various additives on the lipase from Burkholderia cepacia (BcL) immobilized on mixed-function-grafted mesoporous silica gel support by hydrophobic adsorption and covalent attachment were investigated. Catalytic properties of the immobilized biocatalysts were characterized in kinetic resolution of racemic 1-phenylethanol (rac-1a) and 1-(thiophen-2-yl)ethan-1-ol (rac-1b). Screening of more than 40 additives showed significantly enhanced productivity of immobilized BcL with several additives such as PEGs, oleic acid and polyvinyl alcohol. Effects of substrate concentration and temperature between 0-100 °C on kinetic resolution of rac-1a were studied with the best adsorbed BcLs containing PEG 20 k or PVA 18-88 additives in continuous-flow packed-bed reactor. The optimum temperature of lipase activity for BcL co-immobilized with PEG 20k found at around 30 °C determined in the continuous-flow system increased remarkably to around 80 °C for BcL co-immobilized with PVA 18-88.

  11. Living Additive Manufacturing: Transformation of Parent Gels into Diversely Functionalized Daughter Gels Made Possible by Visible Light Photoredox Catalysis

    PubMed Central

    2017-01-01

    Light-initiated additive manufacturing techniques typically rely on layer-by-layer addition or continuous extraction of polymers formed via nonliving, free radical polymerization methods that render the final materials “dead” toward further monomer insertion; the polymer chains within the materials cannot be reactivated to induce chain extension. An alternative “living additive manufacturing” strategy would involve the use of photocontrolled living radical polymerization to spatiotemporally insert monomers into dormant “parent” materials to generate more complex and diversely functionalized “daughter” materials. Here, we demonstrate a proof-of-concept study of living additive manufacturing using end-linked polymer gels embedded with trithiocarbonate iniferters that can be activated by photoinduced single-electron transfer from an organic photoredox catalyst in solution. This system enables the synthesis of a wide range of chemically and mechanically differentiated daughter gels from a single type of parent gel via light-controlled modification of the parent’s average composition, strand length, and/or cross-linking density. Daughter gels that are softer than their parent, stiffer than their parent, larger but with the same modulus as their parent, thermally responsive, polarity responsive, healable, and weldable are all realized. PMID:28280779

  12. Synthesis and characterization of bifunctional surfaces with tunable functional group pairs

    NASA Astrophysics Data System (ADS)

    Galloway, John M.; Kung, Mayfair; Kung, Harold H.

    2016-06-01

    Grafting of pairs of functional groups onto a silica surface was demonstrated by tethering both terminals of an organochlorosilane precursor molecule, Cl2(CH3)Si(CH2)4(CO)(OSi(i-Pr)2)(CH2)2Si(CH3)Cl2, that possess a cleavable silyl ester bond, onto a silica surface. Hydrolytic cleavage of the silyl ester bond of the grafted molecule resulted in the generation of organized pairs of carboxylic acid and organosilanol groups. This organosilanol moiety was easily transformed into other functional groups through condensation reactions to form, together with the neighboring acid group, pairs such as carboxylic acid/secondary amine, carboxylic acid/pyridine, and carboxylic acid/phosphine. In the case of carboxylic acid/amine pairing, there was evidence of the formation of amide. A sample grafted with amine-carboxylic acid pairs was three times more active (per free amine) than a sample without such pairs for the nitroaldol condensation of 4-nitrobenzaldehyde and nitromethane.

  13. Clinical Evaluation of Functional Vision of +1.5 Diopters near Addition, Aspheric, Rotational Asymmetric Multifocal Intraocular Lens

    PubMed Central

    Khoramnia, Rahmin; Attia, Mary Safwat; Koss, Michael Janusz; Linz, Katharina; Auffarth, Gerd Uwe

    2016-01-01

    Purpose To evaluate postoperative outcomes and visual performance in intermediate distance after implantation of a +1.5 diopters (D) addition, aspheric, rotational asymmetric multifocal intraocular lens (MIOL). Methods Patients underwent bilateral cataract surgery with implantation of an aspheric, asymmetric MIOL with +1.5 D near addition. A complete ophthalmological examination was performed preoperatively and 3 months postoperatively. The main outcome measures were monocular and binocular uncorrected distance visual acuity (UDVA), corrected distance visual acuity (CDVA), uncorrected intermediate visual acuity (UIVA), distance corrected intermediate visual acuity (DCIVA), uncorrected near visual acuity (UNVA) and distance corrected keratometry, and manifest refraction. The Salzburg Reading Desk was used to analyze unilateral and bilateral functional vision with uncorrected and corrected reading acuity, reading distance, reading speed, and the smallest log-scaled print size that could be read effectively at near and intermediate distances. Results The study comprised 60 eyes of 30 patients (mean age, 68.30 ± 9.26 years; range, 34 to 80 years). There was significant improvement in UDVA and CDVA. Mean UIVA was 0.01 ± 0.09 logarithm of the minimum angle of resolution (logMAR) and mean DCIVA was -0.02 ± 0.11 logMAR. In Salzburg Reading Desk analysis for UIVA, the mean subjective intermediate distance was 67.58 ± 8.59 cm with mean UIVA of -0.02 ± 0.09 logMAR and mean word count of 96.38 ± 28.32 words/min. Conclusions The new aspheric, asymmetric, +1.5 D near addition MIOL offers good results for distance visual function in combination with good performance for intermediate distances and functional results for near distance. PMID:27729759

  14. Effect of additive particles on mechanical, thermal, and cell functioning properties of poly(methyl methacrylate) cement

    PubMed Central

    Khandaker, Morshed; Vaughan, Melville B; Morris, Tracy L; White, Jeremiah J; Meng, Zhaotong

    2014-01-01

    The most common bone cement material used clinically today for orthopedic surgery is poly(methyl methacrylate) (PMMA). Conventional PMMA bone cement has several mechanical, thermal, and biological disadvantages. To overcome these problems, researchers have investigated combinations of PMMA bone cement and several bioactive particles (micrometers to nanometers in size), such as magnesium oxide, hydroxyapatite, chitosan, barium sulfate, and silica. A study comparing the effect of these individual additives on the mechanical, thermal, and cell functional properties of PMMA would be important to enable selection of suitable additives and design improved PMMA cement for orthopedic applications. Therefore, the goal of this study was to determine the effect of inclusion of magnesium oxide, hydroxyapatite, chitosan, barium sulfate, and silica additives in PMMA on the mechanical, thermal, and cell functional performance of PMMA. American Society for Testing and Materials standard three-point bend flexural and fracture tests were conducted to determine the flexural strength, flexural modulus, and fracture toughness of the different PMMA samples. A custom-made temperature measurement system was used to determine maximum curing temperature and the time needed for each PMMA sample to reach its maximum curing temperature. Osteoblast adhesion and proliferation experiments were performed to determine cell viability using the different PMMA cements. We found that flexural strength and fracture toughness were significantly greater for PMMA specimens that incorporated silica than for the other specimens. All additives prolonged the time taken to reach maximum curing temperature and significantly improved cell adhesion of the PMMA samples. The results of this study could be useful for improving the union of implant-PMMA or bone-PMMA interfaces by incorporating nanoparticles into PMMA cement for orthopedic and orthodontic applications. PMID:24920906

  15. Novel real function based method to construct heterogeneous porous scaffolds and additive manufacturing for use in medical engineering.

    PubMed

    Yang, Nan; Tian, Yanling; Zhang, Dawei

    2015-11-01

    Heterogeneous porous scaffolds have important applications in biomedical engineering, as they can mimic the structures of natural tissues to achieve the corresponding properties. Here, we introduce a new and easy to implement real function based method for constructing complex, heterogeneous porous structures, including hybrid structures, stochastic structures, functionally gradient structures, and multi-scale structures, or their combinations (e.g., hybrid multi-scale structures). Based on micro-CT data, a femur-mimetic structure with gradient morphology was constructed using our method and fabricated using stereolithography. Results showed that our method could generate gradient porosity or gradient specific surfaces and be sufficiently flexible for use with micro-CT data and additive manufacturing (AM) techniques.

  16. Gas-phase reactivity of carboxylic acid functional groups with carbodiimides.

    PubMed

    Prentice, Boone M; Gilbert, Joshua D; Stutzman, John R; Forrest, William P; McLuckey, Scott A

    2013-01-01

    Gas-phase modification of carboxylic acid functionalities is performed via ion/ion reactions with carbodiimide reagents [N-cyclohexyl-N'-(2-morpholinoethyl)carbodiimide (CMC) and [3-(3-Ethylcarbodiimide-1-yl)propyl]trimethylaminium (ECPT)]. Gas-phase ion/ion covalent chemistry requires the formation of a long-lived complex. In this instance, the complex is stabilized by an electrostatic interaction between the fixed charge quaternary ammonium group of the carbodiimide reagent cation and the analyte dianion. Subsequent activation results in characteristic loss of an isocyanate derivative from one side of the carbodiimide functionality, a signature for this covalent chemistry. The resulting amide bond is formed on the analyte at the site of the original carboxylic acid. Reactions involving analytes that do not contain available carboxylic acid groups (e.g., they have been converted to sodium salts) or reagents that do not have the carbodiimide functionality do not undergo a covalent reaction. This chemistry is demonstrated using PAMAM generation 0.5 dendrimer, ethylenediaminetetraacetic acid (EDTA), and the model peptide DGAILDGAILD. This work demonstrates the selective gas-phase covalent modification of carboxylic acid functionalities.

  17. Evidence supporting the importance of microbial functional groups in decomposition models

    NASA Astrophysics Data System (ADS)

    Todd-Brown, K. E.; Lu, L.; Allison, S. D.

    2010-12-01

    Microbial communities mediate organic carbon decomposition in both soil and marine environments. Decomposition depends on microbes that produce extracellular enzymes to degrade complex organic matter, as well as microbes that mineralize simple organic matter to CO2. Therefore microbes could be represented in Earth system models as functional groups based on the extracellular enzymes they produce. However, the importance of including the functional diversity of microbes in decomposition models has been unclear. In this study we simulated microbial functional diversity with two strains of Pseudomonas fluorescens bacteria, one of which secretes extracellular protease and one that does not. These two strains were competed on several carbon resources including casein-glucose, casamino acids-glucose and glucose over several days. We then fit a series of models to the resulting data: 1) an explicit model representing both biomass and substrate pools, 2) a simplified substrate pool model with two biomass pools and one substrate pool, 3) a simplified biomass pool model with one biomass and two substrate pools, 4) a simplified biomass/substrate pool model with one biomass and one substrate pool, and 5) a single carbon pool model. We found that the explicit model (#1) fit the laboratory data significantly better than the other models, suggesting that functional groups and substrate pools should be represented in global decomposition models with time steps on the order of hours.

  18. A meta‐analysis of functional group responses to forest recovery outside of the tropics

    PubMed Central

    Ezard, Thomas H. G.; Martin, Philip A.; Newton, Adrian C.; Doncaster, C. Patrick

    2015-01-01

    Abstract Both active and passive forest restoration schemes are used in degraded landscapes across the world to enhance biodiversity and ecosystem service provision. Restoration is increasingly also being implemented in biodiversity offset schemes as compensation for loss of natural habitat to anthropogenic development. This has raised concerns about the value of replacing old‐growth forest with plantations, motivating research on biodiversity recovery as forest stands age. Functional diversity is now advocated as a key metric for restoration success, yet it has received little analytical attention to date. We conducted a meta‐analysis of 90 studies that measured differences in species richness for functional groups of fungi, lichens, and beetles between old‐growth control and planted or secondary treatment forests in temperate, boreal, and Mediterranean regions. We identified functional‐group–specific relationships in the response of species richness to stand age after forest disturbance. Ectomycorrhizal fungi averaged 90 years for recovery to old‐growth values (between 45 years and unrecoverable at 95% prediction limits), and epiphytic lichens took 180 years to reach 90% of old‐growth values (between 140 years and never for recovery to old‐growth values at 95% prediction limits). Non‐saproxylic beetle richness, in contrast, decreased as stand age of broadleaved forests increased. The slow recovery by some functional groups essential to ecosystem functioning makes old‐growth forest an effectively irreplaceable biodiversity resource that should be exempt from biodiversity offsetting initiatives. PMID:26040756

  19. Various fates of neuronal progenitor cells observed on several different chemical functional groups

    NASA Astrophysics Data System (ADS)

    Liu, Xi; Wang, Ying; He, Jin; Wang, Xiu-Mei; Cui, Fu-Zhai; Xu, Quan-Yuan

    2011-12-01

    Neuronal progenitor cells cultured on gold-coated glass surfaces modified by different chemical functional groups, including hydroxyl (-OH), carboxyl (-COOH), amino (-NH2), bromo (-Br), mercapto (-SH), - Phenyl and methyl (-CH3), were studied here to investigate the influence of surface chemistry on the cells' adhesion, morphology, proliferation and functional gene expression. Focal adhesion staining indicated in the initial culture stage cells exhibited morphological changes in response to different chemical functional groups. Cells cultured on -NH2 grafted surface displayed focal adhesion plaque and flattened morphology and had the largest contact area. However, their counter parts on -CH3 grafted surface displayed no focal adhesion and rounded morphology and had the smallest contact area. After 6 days culture, the proliferation trend was as follows: -NH2 > -SH> -COOH> - Phenyl > - Br > -OH> -CH3. To determine the neural functional properties of the cells affected by surface chemistry, the expression of glutamate decarboxylase (GAD67), nerve growth factor (NGF) and brainderived neurotrophic factor (BDNF) were characterized. An increase of GAD67 expression was observed on -NH2, -COOH and -SH grafted surfaces, while no increase in NGF and BDNF expression was observed on any chemical surfaces. These results highlight the importance of surface chemistry in the fate determination of neuronal progenitor cells, and suggest that surface chemistry must be considered in the design of biomaterials for neural tissue engineering.

  20. Spectral functions with the density matrix renormalization group: Krylov-space approach for correction vectors

    NASA Astrophysics Data System (ADS)

    Nocera, A.; Alvarez, G.

    2016-11-01

    Frequency-dependent correlations, such as the spectral function and the dynamical structure factor, help illustrate condensed matter experiments. Within the density matrix renormalization group (DMRG) framework, an accurate method for calculating spectral functions directly in frequency is the correction-vector method. The correction vector can be computed by solving a linear equation or by minimizing a functional. This paper proposes an alternative to calculate the correction vector: to use the Krylov-space approach. This paper then studies the accuracy and performance of the Krylov-space approach, when applied to the Heisenberg, the t-J, and the Hubbard models. The cases studied indicate that the Krylov-space approach can be more accurate and efficient than the conjugate gradient, and that the error of the former integrates best when a Krylov-space decomposition is also used for ground state DMRG.

  1. Sequential Linker Installation: Precise Placement of Functional Groups in Multivariate Metal-Organic Frameworks

    SciTech Connect

    Yuan, S; Lu, WG; Chen, YP; Zhang, Q; Liu, TF; Feng, DW; Wang, X; Qin, JS; Zhou, HC

    2015-03-11

    A unique strategy, sequential linker installation (SLI), has been developed to construct multivariate MOFs with functional groups precisely positioned. PCN-700, a Zr-MOF with eight-connected Zr6O4(OH)(8)(H2O)(4) clusters, has been judiciously designed; the Zr-6 clusters in this MOF are arranged in such a fashion that, by replacement of terminal OH-/H2O ligands, subsequent insertion of linear dicarboxylate linkers is achieved. We demonstrate that linkers with distinct lengths and functionalities can be sequentially installed into PCN-700. Single-crystal to single-crystal transformation is realized so that the positions of the subsequently installed linkers are pinpointed via single-crystal X-ray diffraction analyses. This methodology provides a powerful tool to construct multivariate MOFs with precisely positioned functionalities in the desired proximity, which would otherwise be difficult to achieve.

  2. Function of the triceps surae muscle group in low and high arched feet: an exploratory study.

    PubMed

    Branthwaite, Helen; Pandyan, Anand; Chockalingam, Nachiappan

    2012-06-01

    The Achilles tendon has been shown to be comprised of segmental components of tendon arising from the tricpes surae muscle group. Motion of the foot joints in low and high arched feet may induce a change in behaviour of the triceps surae muscle group due to altered strain on the tendon. Surface electromyogram of the medial and lateral gastrocnemius and the soleus muscle from 12 subjects (with 6 low arched and 6 high arched feet) (1:1) was recorded whilst walking at a self selected speed along a 10m walkway. The results showed a high variability in muscle activity between groups with patterns emerging within groups. Soleus was more active in 50% of the low arch feet at forefoot loading and there was a crescendo of activity towards heel lift in 58% of all subjects. This observed variability between groups and foot types emphasises the need for further work on individual anatomical variation and foot function to help in the understanding and management of Achilles tendon pathologies and triceps surae dysfunction.

  3. Functionalized quantum dots induce proinflammatory responses in vitro: the role of terminal functional group-associated endocytic pathways

    NASA Astrophysics Data System (ADS)

    Zhang, Yijuan; Pan, Hong; Zhang, Pengfei; Gao, Ningning; Lin, Yi; Luo, Zichao; Li, Ping; Wang, Ce; Liu, Lanlan; Pang, Daiwen; Cai, Lintao; Ma, Yifan

    2013-06-01

    PEGylation has been applied as an effective strategy of surface functionalization to improve the stability and reduce non-specific binding of quantum dots (QDs). However, its effects on the proinflammatory properties of QDs and the underlying mechanism have not been well elucidated yet. Herein, the proinflammatory effects of PEGylated CdSe/ZnS QDs with an amphiphilic polymer coating (PEG-pQDs) were investigated in human pulmonary epithelial cells and macrophages by evaluating the cytokine/chemokine production. The results showed that the proinflammatory effects of PEG-pQDs were strongly associated with the functional groups (-COOH, -NH2, -OH, and -OCH3) at the end of PEG chain. COOH-PEG-pQDs demonstrated the most proinflammatory effects followed by NH2-PEG-pQDs and HO-PEG-pQDs with CH3O-PEG-pQDs exhibiting the least proinflammatory effects. The proinflammatory effects of PEG-pQDs relied on lipid raft- and class A scavenger receptor (SRA)-dependent endocytic pathways as well as the downstream NF-κB and MAPK signaling cascades. COOH-PEG-pQDs were selectively internalized by lipid raft- and SRA-mediated endocytosis, which consequently activated NF-κB signaling pathway. On the other hand, NH2-PEG-pQDs and HO-PEG-pQDs were mostly internalized via lipid raft-mediated endocytosis, thereby activating p38 MAPK/AP-1 signaling cascades. These data revealed a critical role of terminal functional group-associated endocytic pathways in the proinflammatory responses induced by PEGylated QDs in human pulmonary epithelial cells and macrophages.PEGylation has been applied as an effective strategy of surface functionalization to improve the stability and reduce non-specific binding of quantum dots (QDs). However, its effects on the proinflammatory properties of QDs and the underlying mechanism have not been well elucidated yet. Herein, the proinflammatory effects of PEGylated CdSe/ZnS QDs with an amphiphilic polymer coating (PEG-pQDs) were investigated in human pulmonary epithelial

  4. Immediate postoperative radiotherapy in residual nonfunctioning pituitary adenoma: Beneficial effect on local control without additional negative impact on pituitary function and life expectancy

    SciTech Connect

    Bergh, Alfons C.M. van den . E-mail: a.c.m.van.den.bergh@rt.umcg.nl; Berg, Gerrit van den; Schoorl, Michiel A.; Sluiter, Wim J.; Vliet, Anton M. van der; Hoving, Eelco W.; Szabo, Ben G.; Langendijk, Johannes A.; Wolffenbuttel, Bruce H.R.; Dullaart, Robin P.F.

    2007-03-01

    Purpose: To demonstrate the benefit of immediate postoperative radiotherapy in residual nonfunctioning pituitary adenoma (NFA) in perspective to the need for hormonal substitution and life expectancy. Methods and Materials: Retrospective cohort analysis of 122 patients, operated for NFA between 1979 and 1998. Recurrence was defined as regrowth on computed tomography or magnetic resonance imaging. The occurrence of hormonal deficiencies was defined as the starting date of hormonal substitution therapy. Results: Seventy-six patients had residual NFA after surgery and received immediate postoperative radiotherapy (Group 1); three patients developed a recurrence, resulting in a 95% local control rate at 10 years. Twenty-eight patients had residual NFA after surgery, but were followed by a wait-and-see policy (Group 2). Sixteen developed a recurrence, resulting in a local control rate of 49% at 5 years and 22% at 10 years (p < 0.001 compared with Group 1). There were no differences between Group 1 and 2 regarding the need for substitution with thyroid hormone, glucocorticoids, and sex hormones before first surgery, directly after surgery and at end of follow-up. There were no differences in hormone substitution free survival between Group 1 and Group 2 during the study period after first surgery. Life expectancy was similar in Group 1 and 2, and their median life expectancy did not differ from median life expectancy in the general population. Conclusions: Immediate postoperative radiotherapy provides a marked improvement of local control among patients with residual NFA compared with surgery alone, without an additional deleterious effect on pituitary function and life expectancy.

  5. Changes in the structure and function of microbial communities in drinking water treatment bioreactors upon addition of phosphorus.

    PubMed

    Li, Xu; Upadhyaya, Giridhar; Yuen, Wangki; Brown, Jess; Morgenroth, Eberhard; Raskin, Lutgarde

    2010-11-01

    Phosphorus was added as a nutrient to bench-scale and pilot-scale biologically active carbon (BAC) reactors operated for perchlorate and nitrate removal from contaminated groundwater. The two bioreactors responded similarly to phosphorus addition in terms of microbial community function (i.e., reactor performance), while drastically different responses in microbial community structure were detected. Improvement in reactor performance with respect to perchlorate and nitrate removal started within a few days after phosphorus addition for both reactors. Microbial community structures were evaluated using molecular techniques targeting 16S rRNA genes. Clone library results showed that the relative abundance of perchlorate-reducing bacteria (PRB) Dechloromonas and Azospira in the bench-scale reactor increased from 15.2% and 0.6% to 54.2% and 11.7% after phosphorus addition, respectively. Real-time quantitative PCR (qPCR) experiments revealed that these increases started within a few days after phosphorus addition. In contrast, after phosphorus addition, the relative abundance of Dechloromonas in the pilot-scale reactor decreased from 7.1 to 0.6%, while Zoogloea increased from 17.9 to 52.0%. The results of this study demonstrated that similar operating conditions for bench-scale and pilot-scale reactors resulted in similar contaminant removal performances, despite dramatically different responses from microbial communities. These findings suggest that it is important to evaluate the microbial community compositions inside bioreactors used for drinking water treatment, as they determine the microbial composition in the effluent and impact downstream treatment requirements for drinking water production. This information could be particularly relevant to drinking water safety, if pathogens or disinfectant-resistant bacteria are detected in the bioreactors.

  6. Competition patterns among phytoplankton functional groups: How useful are the complex mathematical models?

    NASA Astrophysics Data System (ADS)

    Zhao, Jingyang; Ramin, Maryam; Cheng, Vincent; Arhonditsis, George B.

    2008-05-01

    Simple models have significant contribution to the development of ecological theory. However, these minimalistic modeling approaches usually focus on a small subset of the causes of a phenomenon and neglect important aspects of system dynamics. In this study, we use a complex aquatic biogeochemical model to examine competition patterns and structural shifts in the phytoplankton community under nutrient enrichment conditions. Our model simulates multiple elemental cycles (org. C, N, P, Si, O), multiple functional phytoplankton (diatoms, green algae and cyanobacteria) and zooplankton (copepods and cladocerans) groups. It also takes into account recent advances in stoichiometric nutrient recycling theory, and the zooplankton grazing term is reformulated to include algal food quality effects on zooplankton assimilation efficiency. The model provided a realistic platform to examine the functional properties (e.g., kinetics, growth strategies, intracellular storage capacity) and the abiotic conditions (temperature, nutrient loading) under which the different phytoplankton groups can dominate or can be competitively excluded in oligo, meso and eutrophic environments. Based on the results of our analysis, the intergroup variability in the minimum cell quota and maximum transport rate at the cell surface for phosphorus along with the group-specific metabolic losses can shape the structure of plankton communities. We also use classification tree analysis to elucidate aspects (e.g., relative differences in the functional group properties, critical values of the abiotic conditions, levels of the other plankton community residents) of the complex interplay among physical, chemical and biological factors that drive epilimnetic plankton dynamics. Finally, our study highlights the importance of improving the mathematical representation of phytoplankton adaptive strategies for resources procurement (e.g., regulation of transport kinetics, effects of transport kinetics on the

  7. Water Desalination through Zeolitic Imidazolate Framework Membranes: Significant Role of Functional Groups.

    PubMed

    Gupta, Krishna M; Zhang, Kang; Jiang, Jianwen

    2015-12-08

    A molecular simulation study is reported for water desalination through five zeolitic imidazolate framework (ZIF) membranes, namely ZIF-25, -71, -93, -96, and -97. The five ZIFs possess identical rho-topology but differ in functional groups. The rejection of salt (NaCl) is found to be around 97% in ZIF-25, and 100% in the other four ZIFs. The permeance ranges from 27 to 710 kg/(m(2)·h·bar), about one∼two orders of magnitude higher compared with commercial reverse osmosis membranes. Due to a larger aperture size da, ZIF-25, -71, and -96 exhibit a much higher water flux than ZIF-93 and -97; however, the flux in ZIF-25, -71, and -96 is governed by the polarity of functional group rather than da. With the hydrophobic CH3 group, ZIF-25 has the highest flux despite the smallest da among ZIF-25, -71, and -96. The lifetime of hydrogen bonding in ZIF-25 is shorter than that in ZIF-71 and -96. Furthermore, water molecules undergo a fast flushing motion in ZIF-25, but frequent jumping in ZIF-96 and particularly in ZIF-97. An Arrhenius-type relationship is found between water flux in ZIF-25 and temperature, and the activation energy is predicted to be 6.5 kJ/mol. This simulation study provides a microscopic insight into water desalination in a series of ZIFs, reveals the key factors (aperture size and polarity of functional group) governing water flux, and suggests that ZIF-25 might be an interesting reverse osmosis membrane for high-performance water desalination.

  8. Understanding the effects of a multi-functionalized additive on the cathode-electrolyte interfacial stability of Ni-rich materials

    NASA Astrophysics Data System (ADS)

    Yim, Taeeun; Kang, Kyoung Seok; Mun, Junyoung; Lim, Sang Hoo; Woo, Sang-Gil; Kim, Ki Jae; Park, Min-Sik; Cho, Woosuk; Song, Jun Ho; Han, Young-Kyu; Yu, Ji-Sang; Kim, Young-Jun

    2016-01-01

    Nickel-rich lithium nickel cobalt manganese oxides have received considerable attention as a promising cathode material, however, they have suffered from poor interfacial stability, especially at high temperature. Here, we suggest a bi-functionalized divinyl sulfone that enhances the applicability of a nickel-rich cathode via stabilization of the electrolyte-electrode interface. The divinyl sulfone forms a protective layer on the cathode surface by electrochemical oxidation reactions and this greatly decreases the internal pressure of the cell via stabilization of the Ni-rich cathode-electrolyte interface. The cell controlled with divinyl sulfone shows remarkable cycling performance with 91.9% capacity retention at elevated temperature even after 100 cycles. Additional electrode analyses and first-principles calculations provide critical spectroscopic evidences to demonstrate the combined effects of the sulfone and vinyl functional groups. Once the divinyl sulfone is electrochemically oxidized, the vinyl functional groups readily participate in further stabilizing sulfone-based solid electrolyte interphase intermediates and afford a durable protective layer on the nickel-rich electrode surface.

  9. Effects of Plant Diversity, Functional Group Composition, and Fertilization on Soil Microbial Properties in Experimental Grassland

    PubMed Central

    Strecker, Tanja; Barnard, Romain L.; Niklaus, Pascal A.; Scherer-Lorenzen, Michael; Weigelt, Alexandra; Scheu, Stefan; Eisenhauer, Nico

    2015-01-01

    Background Loss of biodiversity and increased nutrient inputs are two of the most crucial anthropogenic factors driving ecosystem change. Although both received considerable attention in previous studies, information on their interactive effects on ecosystem functioning is scarce. In particular, little is known on how soil biota and their functions are affected by combined changes in plant diversity and fertilization. Methodology/Principal Findings We investigated the effects of plant diversity, functional community composition, and fertilization on the biomass and respiration of soil microbial communities in a long-term biodiversity experiment in semi-natural grassland (Jena Experiment). Plant species richness enhanced microbial basal respiration and microbial biomass, but did not significantly affect microbial specific respiration. In contrast, the presence of legumes and fertilization significantly decreased microbial specific respiration, without altering microbial biomass. The effect of legumes was superimposed by fertilization as indicated by a significant interaction between the presence of legumes and fertilization. Further, changes in microbial stoichiometry (C-to-N ratio) and specific respiration suggest the presence of legumes to reduce N limitation of soil microorganisms and to modify microbial C use efficiency. Conclusions/Significance Our study highlights the role of plant species and functional group diversity as well as interactions between plant community composition and fertilizer application for soil microbial functions. Our results suggest soil microbial stoichiometry to be a powerful indicator of microbial functioning under N limited conditions. Although our results support the notion that plant diversity and fertilizer application independently affect microbial functioning, legume effects on microbial N limitation were superimposed by fertilization, indicating significant interactions between the functional composition of plant communities and

  10. Response of Functional Structure of Soil Microbial Community to Multi-level Nitrogen Additions on the Central Tibetan Plateau

    NASA Astrophysics Data System (ADS)

    Zhang, G.; Yuan, Y.

    2015-12-01

    The use of fossil fuels and fertilizers has increased the amount of biologically reactive nitrogen in the atmosphere over the past century. Tibet is the one of the most threatened regions by nitrogen deposition, thus understanding how its microbial communities function maybe of high importance to predicting microbial responses to nitrogen deposition. Here we describe a short-time nitrogen addition conducted in an alpine steppe ecosystem to investigate the response of functional structure of soil microbial community to multi-level nitrogen addition. Using a GeoChip 4.0, we showed that functional diversities and richness of functional genes were unchanged at low level of nitrogen fertilizer inputs (<20 kg N ha-1 yr-1), but significantly decreased at higher nitrogen fertilizer inputs (>=40 kg N ha-1 yr-1). Detrended correspondence analysis indicated that the functional structure of microbial communities was markedly different across the nitrogen gradients. Most C degradation genes whose abundances significantly increased under elevated N fertilizer were those involved in the degradation of relatively labile C (starch, hemicellulose, cellulose), whereas the abundance of certain genes involved in the degradation of recalcitrant C (i.e. lignin) was largely decreased (such as manganese peroxidase, mnp). The results suggest that the elevated N fertilization rates might significantly accelerate the labile C degradation, but might not spur recalcitrant C degradation. The combined effect of gdh and ureC genes involved in N cycling appeared to shift the balance between ammonia and organic N toward organic N ammonification and hence increased the N mineralization potential. Moreover, Urease directly involved in urea mineralization significantly increased. Lastly, Canonical correspondence analysis showed that soil (TOC+NH4++NO3-+NO2-+pH) and plant (Aboveground plant productivity + Shannon Diversity) variables could explain 38.9% of the variation of soil microbial community

  11. Cell-specific CO2 fixation rates of two distinct groups of plastidic protists in the Atlantic Ocean remain unchanged after nutrient addition.

    PubMed

    Grob, Carolina; Jardillier, Ludwig; Hartmann, Manuela; Ostrowski, Martin; Zubkov, Mikhail V; Scanlan, David J

    2015-04-01

    To assess the role of open-ocean ecosystems in global CO2 fixation, we investigated how picophytoplankton, which dominate primary production, responded to episodic increases in nutrient availability. Previous experiments have shown nitrogen alone, or in combination with phosphorus or iron, to be the proximate limiting nutrient(s) for total phytoplankton grown over several days. Much less is known about how nutrient upshift affects picophytoplankton CO2 fixation over the duration of the light period. To address this issue, we performed a series of small volume (8-60 ml) - short term (10-11 h) nutrient addition experiments in different regions of the Atlantic Ocean using NH4 Cl, FeCl3 , K medium, dust and nutrient-rich water from 300 m depth. We found no significant nutrient stimulation of group-specific CO2 fixation rates of two taxonomically and size-distinct groups of plastidic protists. The above was true regardless of the region sampled or nutrient added, suggesting that this is a generic phenomenon. Our findings show that at least in the short term (i.e. daylight period), nutrient availability does not limit CO2 fixation by the smallest plastidic protists, while their taxonomic composition does not determine their response to nutrient addition.

  12. Thermodynamic characterization of the biocompatible ionic liquid effects on protein model compounds and their functional groups.

    PubMed

    Attri, Pankaj; Venkatesu, Pannuru

    2011-04-14

    The stability of proteins under co-solvent conditions is dependant on the nature of the co-solvent; the co-solvent can alter a protein's properties and structural effects through bimolecular interactions between its functional groups and co-solvent particles. Ionic liquids (ILs) represent a rather diverse class of co-solvents that are combinations of different ions, which are liquids at or close to room temperature. To quantify the bimolecular interactions of protein functional groups with biocompatible ILs, we report the systematic and quantitative apparent transfer free energies (ΔG'(tr)) of a homologous series of cyclic dipeptides (CDs) from water to aqueous solutions of ILs through solubility measurements, as a function of IL concentration at 25 °C under atmospheric pressure. The materials investigated in the present work included the CDs of cyclo(Gly-Gly), cyclo(Ala-Gly), cyclo(Ala-Ala), cyclo(Leu-Ala), and cyclo(Val-Val). The ILs used such as diethylammonium acetate ([Et(2)NH][CH(3)COO], DEAA), triethylammonium acetate ([Et(3)NH][CH(3)COO], TEAA), diethylammonium dihydogen phosphate ([Et(3)NH][H(2)PO(4)], DEAP), triethylammonium dihydogen phosphate ([Et(3)NH][H(2)PO(4)], TEAP), diethylammonium sulfate ([Et(3)NH][HSO(4)], DEAS) and triethylammonium sulfate ([Et(3)NH][HSO(4)], TEAS). We observed positive values of ΔG'(tr) for CDs from water to ILs, indicating that interactions between ILs and CDs are unfavourable, which leads to stabilization of the native structure of CDs. The experimental results were further used for estimating the transfer free energies (Δg'(tr)) of the peptide bond (-CONH-), the peptide backbone unit (-CH(2)C=ONH-), and various functional groups from water to IL solutions. Our results explicitly elucidate that a series of all ammonium ILs act as stabilizers for tested model compounds through the exclusion of ILs from CDs surface.

  13. Improving plant functional groups for dynamic models of biodiversity: at the crossroads between functional and community ecology

    PubMed Central

    Isabelle, Boulangeat; Pauline, Philippe; Sylvain, Abdulhak; Roland, Douzet; Luc, Garraud; Sébastien, Lavergne; Sandra, Lavorel; Jérémie, Van Es; Pascal, Vittoz; Wilfried, Thuiller

    2013-01-01

    The pace of on-going climate change calls for reliable plant biodiversity scenarios. Traditional dynamic vegetation models use plant functional types that are summarized to such an extent that they become meaningless for biodiversity scenarios. Hybrid dynamic vegetation models of intermediate complexity (hybrid-DVMs) have recently been developed to address this issue. These models, at the crossroads between phenomenological and process-based models, are able to involve an intermediate number of well-chosen plant functional groups (PFGs). The challenge is to build meaningful PFGs that are representative of plant biodiversity, and consistent with the parameters and processes of hybrid-DVMs. Here, we propose and test a framework based on few selected traits to define a limited number of PFGs, which are both representative of the diversity (functional and taxonomic) of the flora in the Ecrins National Park, and adapted to hybrid-DVMs. This new classification scheme, together with recent advances in vegetation modeling, constitutes a step forward for mechanistic biodiversity modeling. PMID:24403847

  14. Male mice housed in groups engage in frequent fighting and show a lower response to additional bone loading than females or individually housed males that do not fight.

    PubMed

    Meakin, Lee B; Sugiyama, Toshihiro; Galea, Gabriel L; Browne, William J; Lanyon, Lance E; Price, Joanna S

    2013-05-01

    Experiments to investigate bone's physiological adaptation to mechanical loading frequently employ models that apply dynamic loads to bones in vivo and assess the changes in mass and architecture that result. It is axiomatic that bones will only show an adaptive response if the applied artificial loading environment differs in a significant way from that to which the bones have been habituated by normal functional loading. It is generally assumed that this normal loading is similar between experimental groups. In the study reported here we found that this was not always the case. Male and female 17-week-old C57BL/6 mice were housed in groups of six, and a single episode (40 cycles) of non-invasive axial loading, engendering 2,200 με on the medial surface of the proximal tibiae in sample mice, was applied to right tibiae on alternate days for two weeks. This engendered an adaptive increase in bone mass in females, but not males. Observation revealed the main difference in behaviour between males and females was that males were involved in fights 1.3 times per hour, whereas the females never fought. We therefore housed all mice individually. In females, there was a similar significant osteogenic response to loading in cortical and trabecular bone of both grouped and individual mice. In contrast, in males, adaptive increases in the loaded compared with non-loaded control bones was only apparent in animals housed individually. Our interpretation of these findings is that the frequent vigorous fighting that occurs between young adult males housed in groups could be sufficient to engender peak strains and strain rates that equal or exceed the stimulus derived from artificial loading. This indicates the importance of ensuring that physical activity is consistent between groups. Reducing the background level of the naturally engendered strain environment allows adaptive responses to artificial loading to be demonstrated at lower loads.

  15. Tree Diametric Increment and Litterfall Production in an Eastern Amazonian Forest: the Role of Functional Groups

    NASA Astrophysics Data System (ADS)

    Camargo, P. B. D.; Ferreira, M. L.; Oliveira Junior, R. C.; Saleska, S. R.

    2014-12-01

    Tree growth is a biotic variable of great importance in understanding the dynamics of tree communities and may be used as a tool in studies of biological or climate modeling. Some climate models predict more recurrent climate anomalies in this century, which may alter the functioning of tropical forests with serious structural and demographic implications. The present study aimed to evaluate the profile of tree growth and litterfall production in an eastern Amazon forest, which has suffered recent climatic disturbances. We contrasted different functional groups based on wood density (stem with 0.55; 0.56-0.7; >0.7 g cm-3), light availability (crown illumination index; high illuminated crown - IIC1 until shaded crown - IIC5), and, size class (trees 10-22.5; 22.6-35; 35.1-55; 55,1-90; >90 cm dbh). Tree diameter increment was monthly measured from November 2011 to September 2013 by using dendrometer bands installed on 850 individuals from different families. Litterfall was collected in 64 circular traps, oven dried and weighed, separated into leaves, twigs, reproductive parts and miscellaneous. During the rainy season the sampled trees had the highest rates of tree diametric increment. When analyzing the data by functional groups, large trees had faster growth, but when grouped by wood density, trees with wood density up to 0.55 and between 0.56 and 0.7 g cm-3 had the fastest rates of growth. When grouped by crown illumination index, trees exposed to higher levels of light grew more in comparison to partially shaded trees. Maximum daily air temperature and precipitation were the most important environmental variables in determining the diametric increment profile of the trees. Litterfall production was estimated to be 7.1 Mg ha-1.year-1 and showed a strong seasonal pattern, with dry season production being higher than in the rainy season. Leaves formed the largest fraction of the litterfall, followed by twigs, reproductive parts, and finally miscellaneous. These

  16. Production and characterization of alien chromosome additions in shallot (Allium cepa L. Aggregatum group) carrying extra chromosome(s) of Japanese bunching onion (A. fistulosum L.).

    PubMed

    Hang, Tran Thi Minh; Shigyo, Masayoshi; Yamauchi, Naoki; Tashiro, Yosuke

    2004-10-01

    First and second backcrosses of amphidiploid hybrids (2n = 4x = 32, genomes AAFF) between shallot (Allium cepa Aggregatum group) and A. fistulosum were conducted to produce A. cepa - A. fistulosum alien addition lines. When shallot (A. cepa Aggregatum group) was used as a pollinator, the amphidiploids and allotriploids set germinable BC(1) and BC(2) seeds, respectively. The 237 BC(1) plants mainly consisted of 170 allotriploids (2n = 3x = 24, AAF) and 42 hypo-allotriploids possessing 23 chromosomes, i.e., single-alien deletions (2n = 3x-1 = 23, AAF-nF). The single-alien deletions in the BC(1) progeny showed dwarfing characteristics and were discriminated from the allotriploids (2n = 24) and hyper-allotriploids (2n = 25) by means of flow cytometric analysis. The chromosome numbers of 46 BC(2) seedlings varied from 16 to 24. Eight monosomic additions (2n = 2x+1 = 17, AA+nF) and 20 single-alien deletions were found in these BC(2) seedlings. Consequently, six kinds of A. cepa - A. fistulosum alien chromosome additions possessing different chromosome numbers (2n = 17, 18, 20, 21, 22, 23) were recognized in the BC(1) and BC(2) populations. A total of 79 aneuploids, including 62 single-alien deletions, were analyzed by a chromosome 6F-specific isozyme marker (Got-2) in order to recognize its existence in their chromosome complements. This analysis revealed that two out of 62 single-alien deletions did not possess 6F. One (AAF-6F) out of the possible eight single-alien deletions could be identified at first. The present study is a first step toward the development of a useful tool, such as a complete set of eight different single-alien deletions, for the rapid chromosomal assignment of genes and genetic markers in A. fistulosum.

  17. Polycomb Group (PcG) Proteins and Human Cancers: Multifaceted Functions and Therapeutic Implications

    PubMed Central

    Wang, Wei; Qin, Jiang-Jiang; Voruganti, Sukesh; Nag, Subhasree; Zhou, Jianwei; Zhang, Ruiwen

    2016-01-01

    Polycomb group (PcG) proteins are transcriptional repressors that regulate several crucial developmental and physiological processes in the cell. More recently, they have been found to play important roles in human carcinogenesis and cancer development and progression. The deregulation and dysfunction of PcG proteins often lead to blocking or inappropriate activation of developmental pathways, enhancing cellular proliferation, inhibiting apoptosis, and increasing the cancer stem cell population. Genetic and molecular investigations of PcG proteins have long been focused on their PcG functions. However, PcG proteins have recently been shown to exert non-polycomb functions, contributing to the regulation of diverse cellular functions. We and others have demonstrated that PcG proteins regulate the expression and function of several oncogenes and tumor suppressor genes in a PcG-independent manner, and PcG proteins are associated with the survival of patients with cancer. In this review, we summarize the recent advances in the research on PcG proteins, including both the polycomb-repressive and non-polycomb functions. We specifically focus on the mechanisms by which PcG proteins play roles in cancer initiation, development, and progression. Finally, we discuss the potential value of PcG proteins as molecular biomarkers for the diagnosis and prognosis of cancer, and as molecular targets for cancer therapy. PMID:26227500

  18. Functional relationships between leaf hydraulics and leaf economic traits in response to nutrient addition in subtropical tree species.

    PubMed

    Villagra, Mariana; Campanello, Paula I; Bucci, Sandra J; Goldstein, Guillermo

    2013-12-01

    Leaves can be both a hydraulic bottleneck and a safety valve against hydraulic catastrophic dysfunctions, and thus changes in traits related to water movement in leaves and associated costs may be critical for the success of plant growth. A 4-year fertilization experiment with nitrogen (N) and phosphorus (P) addition was done in a semideciduous Atlantic forest in northeastern Argentina. Saplings of five dominant canopy species were grown in similar gaps inside the forests (five control and five N + P addition plots). Leaf lifespan (LL), leaf mass per unit area (LMA), leaf and stem vulnerability to cavitation, leaf hydraulic conductance (K(leaf_area) and K(leaf_mass)) and leaf turgor loss point (TLP) were measured in the five species and in both treatments. Leaf lifespan tended to decrease with the addition of fertilizers, and LMA was significantly higher in plants with nutrient addition compared with individuals in control plots. The vulnerability to cavitation of leaves (P50(leaf)) either increased or decreased with the nutrient treatment depending on the species, but the average P50(leaf) did not change with nutrient addition. The P50(leaf) decreased linearly with increasing LMA and LL across species and treatments. These trade-offs have an important functional significance because more expensive (higher LMA) and less vulnerable leaves (lower P50(leaf)) are retained for a longer period of time. Osmotic potentials at TLP and at full turgor became more negative with decreasing P50(leaf) regardless of nutrient treatment. The K(leaf) on a mass basis was negatively correlated with LMA and LL, indicating that there is a carbon cost associated with increased water transport that is compensated by a longer LL. The vulnerability to cavitation of stems and leaves were similar, particularly in fertilized plants. Leaves in the species studied may not function as safety valves at low water potentials to protect the hydraulic pathway from water stress-induced cavitation

  19. The effect of tin and antimony addition on the performance of dual function cracking catalyst (DFCC) mixtures

    SciTech Connect

    Occelli, M.L. ); Naraghi, S.M.; Krishnan, V.; Suib, S.L. )

    1992-05-01

    In 1976, the Phillips Petroleum Company successfully demonstrated that the addition of certain organo-antimony compounds to a metal-contaminated heavy gas oil reduced the deleterious effects that metals such as Ni and V have on gasoline yields, coke, and hydrogen selectivities. Nickel has little effect on the activity of a fluidized cracking catalyst (FCC) but generates large amounts of gases, placing severe demands on capabilities of gas compressors. Marketed by Phillips Petroleum Company. Phil-Ad CA antimony organics have been shown to reduce by 50% gas formation due to metal contaminants, especially nickel. However, Sb, when introduced into a fluidized cracking unit, could reduce and form SbH[sub 3], stibine, that like arsine (AsH[sub 3]) is a highly toxic compound. Procedures for the safe usage of Sb in refining operations have been outlined; when used properly, Sb-containing passivating agents did not generate any detectable stibine. Recently, it has been reported that at microactivity test conditions, the additions of diluents (such as aluminas and layered magnesium silicates) capable of selectively sorbing metal contaminants from gas oils can form dual function cracking catalysts (DFCC) that retain most of their useful cracking activity even in the presence of as much as 1.0-1.5% V. It is the purpose of this paper to report the stability of Sb- and Sn-loaded alumina particles and the effects that the addition of metal passivation compounds such as Sb and Sn have on the performance of DFCC mixtures.

  20. Bronchodilator activity of xanthine derivatives substituted with functional groups at the 1- or 7-position.

    PubMed

    Miyamoto, K; Yamamoto, Y; Kurita, M; Sakai, R; Konno, K; Sanae, F; Ohshima, T; Takagi, K; Hasegawa, T; Iwasaki, N

    1993-05-14

    Xanthine derivatives with several functional groups at the 1- or 7-position were synthesized, and their pharmacological activities in guinea pigs were studied. In general, the in vitro tracheal relaxant action and positive chronotropic action of 3-propylxanthines were increased by substitutions with nonpolar functional groups at the 1-position, but decreased by any substitution at the 7-position. On the other hand, because positive chronotropic actions of substituents with allyl, aminoalkyl, alkoxyalkyl, and normal alkyl groups were much less than tracheal muscle became very high with substitutions of 3'-butenyl, (dimethylamino)ethyl, 2'-ethoxyethyl, 3'-methoxypropyl, and n-propyl groups at the 1-position and of 2'-ethoxyethyl, 2'-oxopropyl, and n-propyl groups at the 7-position, compared with theophylline and the corresponding unsubstituted xanthines, 3-propylxanthine and 1-methyl-3-propylxanthine. When compounds were intraduodenally administered to the guinea pig, 1-(2'-ethoxyethyl)-, 1-(3'-methoxypropyl)-, 1-(3'-butenyl)-, and 1-[(dimethylamino)-ethyl]-3-propylxanthines, 1-methyl-7-(2'-oxopropyl)-3-propylxanthine, and denbufylline (1,3-di-n-butyl-7-(2'-oxopropyl)xanthine) effectively inhibited the acetylcholine-induced bronchospasm without heart stimulation or central nervous system-stimulation at the effective dosage range. Particularly, the bronchodilatory effect of 1-(2'-ethoxyethyl)-3-propylxanthine was much stronger and more continuous than those of theophylline and pentoxifylline. On the other hand, there were certain relationships among the in vitro tracheal relaxant activities of these compounds, their affinities for adenosine (A1) receptors in the brain membrane, and their inhibition of cyclic AMP-phosphodiesterase (PDE) in the tracheal muscle. The affinity for A2 receptors of these compounds was very low or negligible. This suggests that both the action on A1 receptors or interaction with adenosine and the cyclic AMP-PDE inhibitory activity contribute

  1. Littelmann path model for geometric crystals, Whittaker functions on Lie groups and Brownian motion

    NASA Astrophysics Data System (ADS)

    Chhaibi, Reda

    2013-02-01

    Generally speaking, this thesis focuses on the interplay between the representations of Lie groups and probability theory. It subdivides into essentially three parts. In a first rather algebraic part, we construct a path model for geometric crystals in the sense of Berenstein and Kazhdan, for complex semi-simple Lie groups. We will mainly describe the algebraic structure, its natural morphisms and parameterizations. The theory of total positivity will play a particularly important role. Then, we anticipate on the probabilistic part by exhibiting a canonical measure on geometric crystals. It uses as ingredients the superpotential for the flag manifold and a measure invariant under the crystal actions. The image measure under the weight map plays the role of Duistermaat-Heckman measure. Its Laplace transform defines Whittaker functions, providing an interesting formula for all Lie groups. Then it appears clearly that Whittaker functions are to geometric crystals, what characters are to combinatorial crystals. The Littlewood-Richardson rule is also exposed. Finally we present the probabilistic approach that allows to find the canonical measure. It is based on the fundamental idea that the Wiener measure will induce the adequate measure on the algebraic structures through the path model. In the last chapter, we show how our geometric model degenerates to the continuous classical Littelmann path model and thus recover known results. For example, the canonical measure on a geometric crystal of highest weight degenerates into a uniform measure on a polytope, and recovers the parameterizations of continuous crystals.

  2. ATR-FTIR characterization of organic functional groups and inorganic ions in ambient aerosols at a rural site

    NASA Astrophysics Data System (ADS)

    Coury, Charity; Dillner, Ann M.

    An Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopic method was used to measure organic functional groups and inorganic ions at Tonto National Monument (TNM), an Interagency Monitoring of Protected Visual Environments (IMPROVE) sampling site in a rural area near Phoenix, Arizona. Functional groups and ions from common aerosol compound classes such as aliphatic and aromatic CH, methylene, methyl, aldehydes/ketones, carboxylic acids, ammonium sulfate and nitrate as well as functional groups from difficult to measure compound classes such as esters/lactones, acid anhydrides, carbohydrate hydroxyl and ethers, amino acids, and amines were quantified. On average, ˜33% of the PM 1.0 mass was composed of organic aerosol. The average (standard deviation) composition of the organic aerosol at TNM was 34% (6%) biogenic functional groups, 21% (5%) oxygenated functional groups, 28% (7%) aliphatic hydrocarbon functional groups (aliphatic CH, methylene and methyl) and 17% (1%) aromatic hydrocarbon functional groups. Compositional analysis, functional group correlations, and back trajectories were used to identify three types of events with source signatures: primary biogenic-influenced, urban-influenced, and regional background. The biogenic-influenced event had high concentrations of amino acids and carbohydrate hydroxyl and ether, as well as aliphatic CH and aromatic CH functional groups and qualitatively high levels of silicate. The urban-influenced events had back trajectories traveling directly from the Phoenix area and high concentrations of hydrocarbons, oxygenated functional groups, and inorganic ions. This aerosol characterization suggests that both primary emissions in Phoenix and secondary formation of aerosols from Phoenix emissions had a major impact on the aerosol composition and concentration at TNM. The regional background source had low concentrations of all functional groups, but had higher concentrations of biogenic functional

  3. Architectural and Functional Diversity of Polycomb Group Response Elements in Drosophila

    PubMed Central

    Brown, J. Lesley; Kassis, Judith A.

    2013-01-01

    Polycomb group response elements (PREs) play an essential role in gene regulation by the Polycomb group (PcG) repressor proteins in Drosophila. PREs are required for the recruitment and maintenance of repression by the PcG proteins. PREs are made up of binding sites for multiple DNA-binding proteins, but it is still unclear what combination(s) of binding sites is required for PRE activity. Here we compare the binding sites and activities of two closely linked yet separable PREs of the Drosophila engrailed (en) gene, PRE1 and PRE2. Both PRE1 and PRE2 contain binding sites for multiple PRE–DNA-binding proteins, but the number, arrangement, and spacing of the sites differs between the two PREs. These differences have functional consequences. Both PRE1 and PRE2 mediate pairing-sensitive silencing of mini-white, a functional assay for PcG repression; however, PRE1 requires two binding sites for Pleiohomeotic (Pho), whereas PRE2 requires only one Pho-binding site for this activity. Furthermore, for full pairing-sensitive silencing activity, PRE1 requires an AT-rich region not found in PRE2. These two PREs behave differently in a PRE embryonic and larval reporter construct inserted at an identical location in the genome. Our data illustrate the diversity of architecture and function of PREs. PMID:23934890

  4. Argos and Spitz group genes function to regulate midline glial cell number in Drosophila embryos.

    PubMed

    Stemerdink, C; Jacobs, J R

    1997-10-01

    The midline glia of the Drosophila embryonic nerve cord undergo a reduction in cell number after facilitating commissural tract morphogenesis. The numbers of midline glia entering apoptosis at this stage can be increased by a loss or reduction of function in genes of the spitz group or Drosophila EGF receptor (DER) pathway. Argos, a secreted molecule with an atypical EGF motif, is postulated to function as a DER antagonist. In this work, we assess the role of argos in the determination of midline glia cell number. Although all midline glia express DER, argos expression is restricted to the midline glia which do not enter apoptosis. Fewer midline glia enter apoptosis in embryos lacking argos function. Ectopic expression of argos is sufficient to remove all DER-expressing midline glia from the nerve cord, even those that already express argos. DER expression is not terminated in the midline glia after spitz group signaling triggers changes in gene expression. It is therefore likely that an attenuation of DER signaling by Argos is integrated with the augmentation of DER signaling by Spitz throughout the period of reduction of midline glia number. We suggest that signaling by Spitz but not Argos is restricted to adhesive junctions. In this manner, midline glia not forming signaling junctions remain sensitive to juxtacrine Argos signaling, while an autocrine Argos signal is excluded by the adhesive junction.

  5. The synthesis of desired functional groups on PEI microgel particles for biomedical and environmental applications

    NASA Astrophysics Data System (ADS)

    Sahiner, Nurettin; Demirci, Sahin; Sahiner, Mehtap; Al-Lohedan, Hamad

    2015-11-01

    Polyethyleneimine (PEI) microgels were synthesized by micro emulsion polymerization technique and converted to positively charged forms by chemical treatments with various modifying agents with different functional groups, such as 2-bromoethanol (-OH), 4-bromobutyronitrile (-CN), 2-bromoethylamine hydrobromide (-NH2), and glycidol (-OH). The functionalization of PEI microgels was confirmed by FT-IR, TGA and zeta potential measurements. Furthermore, a second modification of the modified PEI microgels was induced on 4-bromo butyronitrile-modified PEI microgels (PEI-CN) by amidoximation, to generate new functional groups on the modified PEI microgels. The PEI and modified PEI microgels were also tested for their antimicrobial effects against various bacteria such as Bacillus subtilis ATCC 6633, Escherichia coli ATCC 8739 and Staphylococcus aureus ATCC 25323. Moreover, the PEI-based particles were used for removal of organic dyes such as methyl orange (MO) and congo red (CR). The absorption capacity of PEI-based microgels increased with modification from 101.8 mg/g to 218.8 mg/g with 2-bromoethylamine, 216.2 m/g with 1-bromoethanol, and 224.5 mg/g with 4-bromobutyronitrile for MO. The increase in absorption for CR dyes was from 347.3 mg/g to 390.4 mg/g with 1-bromoethanol, 399.6 mg/g with glycidol, and 349.9 mg/g with 4-bromobutyronitrile.

  6. 1,3-Disubstituted Ureas Functionalized with Ether Groups are Potent Inhibitors of the Soluble Epoxide Hydrolase with Improved Pharmacokinetic Properties

    PubMed Central

    Kim, In-Hae; Tsai, Hsing-Ju; Nishi, Kosuke; Kasagami, Takeo; Morisseau, Christophe; Hammock, Bruce D.

    2008-01-01

    Soluble epoxide hydrolase (sEH) is a therapeutic target for treating hypertension and inflammation. 1,3-Disubstituted ureas functionalized with an ether group are potent sEH inhibitors. However, their relatively low metabolic stability leads to poor pharmacokinetic properties. To improve their bioavailability, we investigated the effect of incorporating various polar groups on the ether function on the inhibition potencies, physical properties, in vitro metabolic stability, and pharmacokinetic properties. The structure-activity relationship (SAR) studies showed that a hydrophobic linker between the urea group and the ether function is necessary to keep their potency. In addition, urea-ether inhibitors having a polar group such as diethylene glycol or morpholine significantly improved their physical properties and metabolic stability without any loss of inhibitory potency. Furthermore, improved pharmacokinetic properties in murine and canine models were obtained with the resulting inhibitors. These findings will facilitate the usage of sEH inhibitors in animal models of hypertension and inflammation. PMID:17894481

  7. Non-parametric estimation of the odds ratios for continuous exposures using generalized additive models with an unknown link function.

    PubMed

    Cadarso-Suárez, Carmen; Roca-Pardiñas, Javier; Figueiras, Adolfo; González-Manteiga, Wenceslao

    2005-04-30

    The generalized additive, model (GAM) is a powerful and widely used tool that allows researchers to fit, non-parametrically, the effect of continuous predictors on a transformation of the mean response variable. Such a transformation is given by a so-called link function, and in GAMs this link function is assumed to be known. Nevertheless, if an incorrect choice is made for the link, the resulting GAM is misspecified and the results obtained may be misleading. In this paper, we propose a modified version of the local scoring algorithm that allows for the non-parametric estimation of the link function, by using local linear kernel smoothers. To better understand the effect that each covariate produces on the outcome, results are expressed in terms of the non-parametric odds ratio (OR) curves. Bootstrap techniques were used to correct the bias in the OR estimation and to construct point-wise confidence intervals. A simulation study was carried out to assess the behaviour of the resulting estimates. The proposed methodology was illustrated using data from the AIDS Register of Galicia (NW Spain), with a view to assessing the effect of the CD4 lymphocyte count on the probability of being AIDS-diagnosed via Tuberculosis (TB). This application shows how the link's flexibility makes it possible to obtain OR curve estimates that are less sensitive to the presence of outliers and unusual values that are often present in the extremes of the covariate distributions.

  8. 14 CFR Section 11 - Functional Classification-Operating Expenses of Group II and Group III Air Carriers

    Code of Federal Regulations, 2011 CFR

    2011-01-01

    ... operations. b. This subfunction shall not include expenses related to financial accounting, purchasing or... contribute to more than a single operating function such as general financial accounting activities... accounting year. Allocations of maintenance burden to capital projects, and service sales to others shall...

  9. Role of functional groups in fiber in the binding of zinc

    SciTech Connect

    Jiang, K.

    1986-03-01

    The binding of zinc by purified cellulose, xylan, methylated xylan, pectin and methylated pectin was measured in vitro. Methylated xylan and methylated pectin were prepared chemically from xylan and pectin, respectively, to block hydroxyl and carboxyl groups. Comparison of zinc binding capacities was made between xylan and methylated xylan, and between pectin and methylated pectin to assess the role of the two functional groups in binding minerals. The binding of zinc was conducted at pH 2.6, 4.0, 5.4 and 6.8 in various concentrations of ZnSO/sub 4/ solution containing /sup 65/Zn using a dialysis system for water-soluble pectin and an incubation-centrifugation model for the other four water-insoluble fibers. The results showed that zinc binding by each fiber was pH dependent and it increased from pH 2.6 to 6.8 (p < 0.001). At pH 6.8, % Zn bound to fiber decreased as concentration of ZnSO/sub 4/ increased from 1 ..mu..M to 96 ..mu..M (p less than or equal to 0.01). mean zinc binding ratio of pectin to methylated xylan was 5.1, whereas the ratio of pectin t methylated pectin was only 1.7. This suggests that the hydroxyl group in xylan plays a more important role than the carboxyl group in pectin in the binding of zinc.

  10. Submerged vegetation removal promotes shift of dominant phytoplankton functional groups in a eutrophic lake.

    PubMed

    Dong, Jing; Yang, Kai; Li, Shuangshuang; Li, Genbao; Song, Lirong

    2014-08-01

    Historical data indicate that the dominance of submerged plants in Dianchi Lake in the 1960s was characterized by low algal density with dominance of non-toxic group J (Scenedesmus, Pediastrum, etc.). The removal of submerged plants, which began in the 1970s, resulted in the expansion of bloom-forming Microcystis (group M). Laboratory experiments suggested that Microcystis aeruginosa was inclined to grow and develop at elevated temperatures. The growth of Scenedesmus obliquus was slower than that of co-cultivated M. aeruginosa in the absence of Ceratophyllum demersum, especially at higher temperatures. The existence of submerged plant C. demersum could inhibit the growth of the harmful algae M. aeruginosa and this inhibitory effect by C. demersum was enhanced with an increase in temperature. Instead, with C. demersum, the growth of S. obliquus was not inhibited, but the co-cultivated M. aeruginosa was eliminated in a short time. Combined with the historical data and laboratory experiments, it was indicated that the submerged plants might play important roles in the dominance of the non-toxic group J in the historical succession. Consequently, the introduction of the submerged plant such as C. demersum might alter the dominant phytoplankton functional groups from M to J and benefit the restoration of the eutrophic lake.

  11. Mechanistic considerations on contact-active antimicrobial surfaces with controlled functional group densities.

    PubMed

    Bieser, Arno M; Tiller, Joerg C

    2011-04-08

    A series of N-alkyl-N,N-dimethyldeoxyammonium celluloses is synthesized by converting tosyl celluloses with DBA and DDA, respectively. Surface coatings with these water-insoluble derivatives contain well-defined densities of quaternary ammonium functions and nonactive hydrophobic and hydrophilic groups. It is shown that the antimicrobial activity of such surfaces against S. aureus requires a delicate balance between DDA, BDA, and hydrophobic groups. A mechanism is proposed that involves the selective adhesion of anionic phospholipids from the bacterial cell membrane. This so-called phospholipid sponge effect is supported by the fact that all coatings could be deactivated by treatment with SDS or negatively charged phospholipids, but not with neutral phospholipids.

  12. Biomass Vanillin-Derived Polymeric Microspheres Containing Functional Aldehyde Groups: Preparation, Characterization, and Application as Adsorbent.

    PubMed

    Zhang, Huanyu; Yong, Xueyong; Zhou, Jinyong; Deng, Jianping; Wu, Youping

    2016-02-03

    The contribution reports the first polymeric microspheres derived from a biomass, vanillin. It reacted with methacryloyl chloride, providing monomer vanillin methacrylate (VMA), which underwent suspension polymerization in aqueous media and yielded microspheres in high yield (>90 wt %). By controlling the N2 bubbling mode and by optimizing the cosolvent for dissolving the solid monomer, the microspheres were endowed with surface pores, demonstrated by SEM images and mercury intrusion porosimetry measurement. Taking advantage of the reactive aldehyde groups, the microspheres further reacted with glycine, thereby leading to a novel type of Schiff-base chelating material. The functionalized microspheres demonstrated remarkable adsorption toward Cu(2+) (maximum, 135 mg/g) which was taken as representative for metal ions. The present study provides an unprecedented class of biobased polymeric microspheres showing large potentials as adsorbents in wastewater treatment. Also importantly, the reactive aldehyde groups may enable the microspheres to be used as novel materials for immobilizing biomacromolecules, e.g. enzymes.

  13. Natural molecular fragments, functional groups, and holographic constraints on electron densities.

    PubMed

    Mezey, Paul G

    2012-06-28

    One of the tools of the shape analysis of molecular electron densities, the Density Threshold Progression Approach used in Shape Group studies can also serve as a criterion for the selection of "natural" molecular fragments, relevant to functional group comparisons, reactivity studies, as well as to the study of levels of relative "autonomy" of various molecular regions. The relevance of these approaches to the fragment-based studies of large molecules, such as biopolymers and nanostructures is emphasized, and the constraints represented by the holographic electron density theorem to this and alternative recent fragment approaches are discussed. The analogies with potential energy hypersurface analysis using the Energy Threshold Progression Approach and connections to level set methods are discussed, and the common features of these seemingly distant problems are described.

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

    SciTech Connect

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

    2015-01-26

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

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

    DOE PAGES

    Mehio, Nada; Lashely, Mark A.; Nugent, Joseph W.; ...

    2015-01-26

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

  16. Effect of chemical functionalization groups on Zr6-AzoBDC to enhance H2, CH4 storage and CO2 capture: a theoretical investigation

    NASA Astrophysics Data System (ADS)

    Trang, Khung M.; Pham, Hung Q.; Pham-Tran, Nguyen-Nguyen

    2015-09-01

    Grand canonical Monte Carlo (GCMC) simulation combined with the ideal adsorbed solution theory (IAST) and a statistical method were utilized to investigate the effect of functional groups on zirconium oxide based metal-organic frameworks (MOFs) Zr6-AzoBDC (Zr6A) for the gases (H2, CH4) adsorption property and CO2/CH4 selectivity under low pressure. The results showed that phenyl groups containing nitrogen (pyridine, pyrimidine) and thiophene group enhance the gas affinity with MOFs, therefore increasing both gravimetric and volumetric uptake. In addition, this behavior can also cause significantly improved selective capture of CO2 from CO2/CH4 gas mixtures. Among functional groups studied, the sulfonic acid group can potentially improve CH4, CO2 uptake and H2 isosteric heat of adsorption. These findings would play a vital role in designing new materials toward gas adsorption properties.

  17. Effects of biodiversity on the functioning of trophic groups and ecosystems.

    PubMed

    Cardinale, Bradley J; Srivastava, Diane S; Duffy, J Emmett; Wright, Justin P; Downing, Amy L; Sankaran, Mahesh; Jouseau, Claire

    2006-10-26

    Over the past decade, accelerating rates of species extinction have prompted an increasing number of studies to reduce species diversity experimentally and examine how this alters the efficiency by which communities capture resources and convert those into biomass. So far, the generality of patterns and processes observed in individual studies have been the subjects of considerable debate. Here we present a formal meta-analysis of studies that have experimentally manipulated species diversity to examine how it affects the functioning of numerous trophic groups in multiple types of ecosystem. We show that the average effect of decreasing species richness is to decrease the abundance or biomass of the focal trophic group, leading to less complete depletion of resources used by that group. At the same time, analyses reveal that the standing stock of, and resource depletion by, the most species-rich polyculture tends to be no different from that of the single most productive species used in an experiment. Of the known mechanisms that might explain these trends, results are most consistent with what is called the 'sampling effect', which occurs when diverse communities are more likely to contain and become dominated by the most productive species. Whether this mechanism is widespread in natural communities is currently controversial. Patterns we report are remarkably consistent for four different trophic groups (producers, herbivores, detritivores and predators) and two major ecosystem types (aquatic and terrestrial). Collectively, our analyses suggest that the average species loss does indeed affect the functioning of a wide variety of organisms and ecosystems, but the magnitude of these effects is ultimately determined by the identity of species that are going extinct.

  18. Functional renormalization group study of an eight-band model for the iron arsenides

    NASA Astrophysics Data System (ADS)

    Lichtenstein, J.; Maier, S. A.; Honerkamp, C.; Platt, C.; Thomale, R.; Andersen, O. K.; Boeri, L.

    2014-06-01

    We investigate the superconducting pairing instabilities of eight-band models for the iron arsenides. Using a functional renormalization group treatment, we determine how the critical energy scale for superconductivity depends on the electronic band structure. Most importantly, if we vary the parameters from values corresponding to LaFeAsO to SmFeAsO, the pairing scale is strongly enhanced, in accordance with the experimental observation. We analyze the reasons for this trend and compare the results of the eight-band approach to those found using five-band models.

  19. Functional renormalization group study of an 8-band model for the iron arsenides

    NASA Astrophysics Data System (ADS)

    Honerkamp, Carsten; Lichtenstein, Julian; Maier, Stefan A.; Platt, Christian; Thomale, Ronny; Andersen, Ole Krogh; Boeri, Lilia

    2014-03-01

    We investigate the superconducting pairing instabilities of eight-band models for 1111 iron arsenides. Using a functional renormalization group treatment, we determine how the critical energy scale for superconductivity depends on the electronic band structure. Most importantly, if we vary the parameters from values corresponding to LaFeAsO to SmFeAsO, the pairing scale is strongly enhanced, in accordance with the experimental observation. We analyze the reasons for this trend and compare the results of the eight-band approach to those found using five-band models.

  20. On the functional renormalization group approach for Yang-Mills fields

    NASA Astrophysics Data System (ADS)

    Lavrov, Peter M.; Shapiro, Ilya L.

    2013-06-01

    We explore the gauge dependence of the effective average action within the functional renormalization group (FRG) approach. It is shown that in the framework of standard definitions of FRG for the Yang-Mills theory, the effective average action remains gauge-dependent on-shell, independent on the use of truncation scheme. Furthermore, we propose a new formulation of the FRG, based on the use of composite operators. In this case one can provide on-shell gauge-invariance for the effective average action and universality of S-matrix.

  1. Superconductivity of monolayer Mo2C: The key role of functional groups.

    PubMed

    Zhang, Jun-Jie; Dong, Shuai

    2017-01-21

    Monolayer Mo2C is a new member of two-dimensional materials. Here the electronic structure and lattice dynamics of monolayer Mo2C are calculated. According to the electron-phonon interaction, it is predicted that monolayer Mo2C could be a quasi-two-dimensional superconductor and the effects of functional-groups are crucially important considering its unsaturated surface. Despite the suppressed superconductivity by chalcogen adsorption, our most interesting prediction is that the electron-phonon interaction of monolayer Mo2C can be greatly enhanced by bromine absorption, suggesting that Mo2CBr2 as a good candidate for a nanoscale superconductor.

  2. Functional Gene Group Analysis Indicates No Role for Heterotrimeric G Proteins in Cognitive Ability

    PubMed Central

    Davies, Gail; Liewald, David Cherry McLachlan; Payton, Anthony; Craig, Leone C. A.; Whalley, Lawrence J.; Horan, Mike; Ollier, William; Starr, John M.; Pendleton, Neil; Posthuma, Danielle; Bates, Timothy C.; Deary, Ian J.

    2014-01-01

    Previous functional gene group analyses implicated common single nucleotide polymorphisms (SNPs) in heterotrimeric G protein coding genes as being associated with differences in human intelligence. Here, we sought to replicate this finding using five independent cohorts of older adults including current IQ and childhood IQ, and using both gene- and SNP-based analytic strategies. No significant associations were found between variation in heterotrimeric G protein genes and intelligence in any cohort at either of the two time points. These results indicate that, whereas G protein systems are important in cognition, common genetic variation in these genes is unlikely to be a substantial influence on human intelligence differences. PMID:24626473

  3. Superconductivity of monolayer Mo2C: The key role of functional groups

    NASA Astrophysics Data Sy