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Sample records for bond functionalization approach

  1. Atom and Bond Fukui Functions and Matrices: A Hirshfeld-I Atoms-in-Molecule Approach.

    Science.gov (United States)

    Oña, Ofelia B; De Clercq, Olivier; Alcoba, Diego R; Torre, Alicia; Lain, Luis; Van Neck, Dimitri; Bultinck, Patrick

    2016-09-19

    The Fukui function is often used in its atom-condensed form by isolating it from the molecular Fukui function using a chosen weight function for the atom in the molecule. Recently, Fukui functions and matrices for both atoms and bonds separately were introduced for semiempirical and ab initio levels of theory using Hückel and Mulliken atoms-in-molecule models. In this work, a double partitioning method of the Fukui matrix is proposed within the Hirshfeld-I atoms-in-molecule framework. Diagonalizing the resulting atomic and bond matrices gives eigenvalues and eigenvectors (Fukui orbitals) describing the reactivity of atoms and bonds. The Fukui function is the diagonal element of the Fukui matrix and may be resolved in atom and bond contributions. The extra information contained in the atom and bond resolution of the Fukui matrices and functions is highlighted. The effect of the choice of weight function arising from the Hirshfeld-I approach to obtain atom- and bond-condensed Fukui functions is studied. A comparison of the results with those generated by using the Mulliken atoms-in-molecule approach shows low correlation between the two partitioning schemes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Size-extensive wave functions for quantum Monte Carlo: A linear scaling generalized valence bond approach

    NARCIS (Netherlands)

    Fracchia, F.; Filippi, Claudia; Amovilli, C.

    2012-01-01

    We propose a new class of multideterminantal Jastrow–Slater wave functions constructed with localized orbitals and designed to describe complex potential energy surfaces of molecular systems for use in quantum Monte Carlo (QMC). Inspired by the generalized valence bond formalism, we elaborate a

  3. Hydrogen bonding in malonaldehyde: a density functional and reparametrized semiempirical approach

    International Nuclear Information System (INIS)

    Kovacevic, Goran; Hrenar, Tomica; Doslic, Nadja

    2003-01-01

    Intramolecular proton transfer in malonaldehyde (MA) has been investigated by density functional theory (DFT). The DFT results were used for the construction of a high quality semiempirical potential energy surface with a reparametrized PM3 Hamiltonian. A two-step reparameterization procedure is proposed in which (i) the PM3-MAIS core-core functions for the O-H and H-H interactions were used and a new functional form for the O-O correction function was proposed and (ii) a set of specific reaction parameters (SRP) has been obtained via genetic algorithm optimization. The quality of the reparametrized semiempirical potential energy surfaces was tested by calculating the tunneling splitting of vibrational levels and the anharmonic vibrational frequencies of the system. The applicability to multi-dimensional dynamics in large molecular systems is discussed

  4. Recent advances in C-S bond formation via C-H bond functionalization and decarboxylation.

    Science.gov (United States)

    Shen, Chao; Zhang, Pengfei; Sun, Qiang; Bai, Shiqiang; Hor, T S Andy; Liu, Xiaogang

    2015-01-07

    The development of mild and general methods for C-S bond formation has received significant attention because the C-S bond is indispensable in many important biological and pharmaceutical compounds. Early examples for the synthesis of C-S bonds are generally limited to the condensation reaction between a metal thiolate and an organic halide. Recent chemical approaches for C-S bond formation, based upon direct C-H bond functionalization and decarboxylative reactions, not only provide new insights into the mechanistic understanding of C-S coupling reactions but also allow the synthesis of sulfur-containing compounds from more effective synthetic routes with high atom economy. This review intends to explore recent advances in C-S bond formation via C-H functionalization and decarboxylation, and the growing opportunities they present to the construction of complex chemical scaffolds for applications encompassing natural product synthesis, synthetic methodology development, and functional materials as well as nanotechnology.

  5. Signal analysis approach to ultrasonic evaluation of diffusion bond quality

    International Nuclear Information System (INIS)

    Thomas, Graham; Chinn, Diane

    1999-01-01

    Solid state bonds like the diffusion bond are attractive techniques for joining dissimilar materials since they are not prone to the defects that occur with fusion welding. Ultrasonic methods can detect the presence of totally unbonded regions but have difficulty sensing poor bonded areas where the substrates are in intimate contact. Standard ultrasonic imaging is based on amplitude changes in the signal reflected from the bond interface. Unfortunately, amplitude alone is not sensitive to bond quality. We demonstrated that there is additional information in the ultrasonic signal that correlates with bond quality. In our approach, we interrogated a set of dissimilar diffusion bonded samples with broad band ultrasonic signals. The signals were digitally processed and the characteristics of the signals that corresponded to bond quality were determined. These characteristics or features were processed with pattern recognition algorithms to produce predictions of bond quality. The predicted bond quality was then compared with the destructive measurement to assess the classification capability of the ultrasonic technique

  6. Automating Partial Period Bond Valuation with Excel's Day Counting Functions

    Science.gov (United States)

    Vicknair, David; Spruell, James

    2009-01-01

    An Excel model for calculating the actual price of bonds under a 30 day/month, 360 day/year day counting assumption by nesting the DAYS360 function within the PV function is developed. When programmed into an Excel spreadsheet, the model can accommodate annual and semiannual payment bonds sold on or between interest dates using six fundamental…

  7. Carbon-Oxygen Hydrogen Bonding in Biological Structure and Function

    Science.gov (United States)

    Horowitz, Scott; Trievel, Raymond C.

    2012-01-01

    Carbon-oxygen (CH···O) hydrogen bonding represents an unusual category of molecular interactions first documented in biological structures over 4 decades ago. Although CH···O hydrogen bonding has remained generally underappreciated in the biochemical literature, studies over the last 15 years have begun to yield direct evidence of these interactions in biological systems. In this minireview, we provide a historical context of biological CH···O hydrogen bonding and summarize some major advancements from experimental studies over the past several years that have elucidated the importance, prevalence, and functions of these interactions. In particular, we examine the impact of CH···O bonds on protein and nucleic acid structure, molecular recognition, and enzyme catalysis and conclude by exploring overarching themes and unresolved questions regarding unconventional interactions in biomolecular structure. PMID:23048026

  8. Effect of water storage on resin-dentin bond strengths formed by different bonding approaches

    Directory of Open Access Journals (Sweden)

    Martins G

    2009-01-01

    Full Text Available Objectives: The purpose of this study was to evaluate the influence of water storage on resin-dentin bond strengths [µTBS] using different adhesive bonding approaches. Materials and Methods: Flat superficial dentin surfaces of 24 extracted human third molars were exposed and polished to create a standardized smear layer. The teeth were randomly distributed into four different groups: Three-step etch-and-rinse (Adper Scotchbond Multi-Purpose, 3M ESPE - SBMP, two-step etch-and-rinse (Adper Single Bond 2, 3 M ESPE - SB; two-step self-etch (AdheSE, Ivoclar/Vivadent - AD; and self-etch 1 step (Adper Prompt L-Pop, 3M ESPE - LP. Following the adhesive application (n = 6, resin composite was incrementally applied (Filtek™ Supreme XT - 3 M ESPE in order to obtain bonded sticks, with a cross-sectioned area of 0.81 mm 2 . The bonded sticks were randomly divided and assigned to be tested after one day [OD] (n 30 or six months [6 M] of water storage [6 M] (n = 30. Results: Two-way ANOVA and Tukey′s test showed that none of the adhesives showed degradation after 6 M. SB achieved the highest µTBS both in the [OD] (49.13 MPa and [6M] (40.27 MPa. Despite the highest values in both time evaluations, the µTBS of SB significantly reduced after 6M. LP showed the lowest µTBS in both periods of evaluation (18.35 and 18.34 MPa. Conclusions: Although a significant degradation was only observed for SB, this was the adhesive that showed the highest µTBS after 6 M of water storage.

  9. Extending density functional embedding theory for covalently bonded systems.

    Science.gov (United States)

    Yu, Kuang; Carter, Emily A

    2017-12-19

    Quantum embedding theory aims to provide an efficient solution to obtain accurate electronic energies for systems too large for full-scale, high-level quantum calculations. It adopts a hierarchical approach that divides the total system into a small embedded region and a larger environment, using different levels of theory to describe each part. Previously, we developed a density-based quantum embedding theory called density functional embedding theory (DFET), which achieved considerable success in metals and semiconductors. In this work, we extend DFET into a density-matrix-based nonlocal form, enabling DFET to study the stronger quantum couplings between covalently bonded subsystems. We name this theory density-matrix functional embedding theory (DMFET), and we demonstrate its performance in several test examples that resemble various real applications in both chemistry and biochemistry. DMFET gives excellent results in all cases tested thus far, including predicting isomerization energies, proton transfer energies, and highest occupied molecular orbital-lowest unoccupied molecular orbital gaps for local chromophores. Here, we show that DMFET systematically improves the quality of the results compared with the widely used state-of-the-art methods, such as the simple capped cluster model or the widely used ONIOM method.

  10. Benchmarking Density Functionals for Chemical Bonds of Gold

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2017-01-01

    Gold plays a major role in nanochemistry, catalysis, and electrochemistry. Accordingly, hundreds of studies apply density functionals to study chemical bonding with gold, yet there is no systematic attempt to assess the accuracy of these methods applied to gold. This paper reports a benchmark...... considering the diverse bonds to gold and the complication of relativistic effects. Thus, studies that use DFT with effective core potentials for gold chemistry, with no alternative due to computational cost, are on solid ground using TPSS-D3 or PBE-D3....

  11. An asset pricing approach to liquidity effects in corporate bond markets

    NARCIS (Netherlands)

    Bongaerts, Dion; de Jong, Frank; Driessen, Joost

    We use an asset pricing approach to compare the effects of expected liquidity and liquidity risk on expected U.S. corporate bond returns. Liquidity measures are constructed for bond portfolios using a Bayesian approach to estimate Roll’s measure. The results show that expected bond liquidity and

  12. Integration a functional approach

    CERN Document Server

    Bichteler, Klaus

    1998-01-01

    This book covers Lebesgue integration and its generalizations from Daniell's point of view, modified by the use of seminorms. Integrating functions rather than measuring sets is posited as the main purpose of measure theory. From this point of view Lebesgue's integral can be had as a rather straightforward, even simplistic, extension of Riemann's integral; and its aims, definitions, and procedures can be motivated at an elementary level. The notion of measurability, for example, is suggested by Littlewood's observations rather than being conveyed authoritatively through definitions of (sigma)-algebras and good-cut-conditions, the latter of which are hard to justify and thus appear mysterious, even nettlesome, to the beginner. The approach taken provides the additional benefit of cutting the labor in half. The use of seminorms, ubiquitous in modern analysis, speeds things up even further. The book is intended for the reader who has some experience with proofs, a beginning graduate student for example. It might...

  13. Site-selective and stereoselective functionalization of non-activated tertiary C-H bonds

    Science.gov (United States)

    Liao, Kuangbiao; Pickel, Thomas C.; Boyarskikh, Vyacheslav; Bacsa, John; Musaev, Djamaladdin G.; Davies, Huw M. L.

    2017-11-01

    The synthesis of complex organic compounds usually relies on controlling the reactions of the functional groups. In recent years, it has become possible to carry out reactions directly on the C-H bonds, previously considered to be unreactive. One of the major challenges is to control the site-selectivity because most organic compounds have many similar C-H bonds. The most well developed procedures so far rely on the use of substrate control, in which the substrate has one inherently more reactive C-H bond or contains a directing group or the reaction is conducted intramolecularly so that a specific C-H bond is favoured. A more versatile but more challenging approach is to use catalysts to control which site in the substrate is functionalized. p450 enzymes exhibit C-H oxidation site-selectivity, in which the enzyme scaffold causes a specific C-H bond to be functionalized by placing it close to the iron-oxo haem complex. Several studies have aimed to emulate this enzymatic site-selectivity with designed transition-metal catalysts but it is difficult to achieve exceptionally high levels of site-selectivity. Recently, we reported a dirhodium catalyst for the site-selective functionalization of the most accessible non-activated (that is, not next to a functional group) secondary C-H bonds by means of rhodium-carbene-induced C-H insertion. Here we describe another dirhodium catalyst that has a very different reactivity profile. Instead of the secondary C-H bond, the new catalyst is capable of precise site-selectivity at the most accessible tertiary C-H bonds. Using this catalyst, we modify several natural products, including steroids and a vitamin E derivative, indicating the applicability of this method of synthesis to the late-stage functionalization of complex molecules. These studies show it is possible to achieve site-selectivity at different positions within a substrate simply by selecting the appropriate catalyst. We hope that this work will inspire the design of

  14. Direct α-C-H bond functionalization of unprotected cyclic amines

    Science.gov (United States)

    Chen, Weijie; Ma, Longle; Paul, Anirudra; Seidel, Daniel

    2018-02-01

    Cyclic amines are ubiquitous core structures of bioactive natural products and pharmaceutical drugs. Although the site-selective abstraction of C-H bonds is an attractive strategy for preparing valuable functionalized amines from their readily available parent heterocycles, this approach has largely been limited to substrates that require protection of the amine nitrogen atom. In addition, most methods rely on transition metals and are incompatible with the presence of amine N-H bonds. Here we introduce a protecting-group-free approach for the α-functionalization of cyclic secondary amines. An operationally simple one-pot procedure generates products via a process that involves intermolecular hydride transfer to generate an imine intermediate that is subsequently captured by a nucleophile, such as an alkyl or aryl lithium compound. Reactions are regioselective and stereospecific and enable the rapid preparation of bioactive amines, as exemplified by the facile synthesis of anabasine and (-)-solenopsin A.

  15. One period coupon bond valuation with revised first passage time approach and the application in Indonesian corporate bond

    Science.gov (United States)

    Maruddani, Di Asih I.; Rosadi, Dedi; Gunardic, Abdurakhman

    2015-02-01

    The value of a corporate bond is conventionally expressed in terms of zero coupon bond. In practice, the most common form of debt instrument is coupon bond and allows early default before maturity as safety covenant for the bondholder. This paper study valuation for one period coupon bond, a coupon bond that only give one time coupon at the bond period. It assumes that the model give bondholder the right to reorganize a firm if its value falls below a given barrier. Revised first passage time approach is applied for default time rule. As a result, formulas of equity, liability, and probability of default is derived for this specified model. Straightforward integration under risk neutral pricing is used for deriving those formulas. For the application, bond of Bank Rakyat Indonesia (BRI) as one of the largest bank in Indonesia is analyzed. R computing show that value of the equity is IDR 453.724.549.000.000, the liability is IDR 2.657.394.000.000, and the probability if default is 5.645305E-47 %.

  16. Benchmarking Density Functionals for Chemical Bonds of Gold

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2017-01-01

    data set probes all types of bonding to gold from very electronegative halides that force Au+ electronic structure, via covalently bonded systems, hard and soft Lewis acids and bases that either work against or complement the softness of gold, the Au2 molecule probing gold's bond with itself, and weak...

  17. Density functional theory, natural bond orbital and quantum theory of ...

    Indian Academy of Sciences (India)

    The nature of the H-bonds were characterized by the natural bond orbital (NBO) and the quantum theory of atoms in molecule (QTAIM) analyses as well. The intramolecular H-bond formed between the amino and carboxyl oxygen atom of tryptophan was retained in most of the complexes, and the cooperativity between the ...

  18. Energy decomposition analysis of single bonds within Kohn-Sham density functional theory.

    Science.gov (United States)

    Levine, Daniel S; Head-Gordon, Martin

    2017-11-28

    An energy decomposition analysis (EDA) for single chemical bonds is presented within the framework of Kohn-Sham density functional theory based on spin projection equations that are exact within wave function theory. Chemical bond energies can then be understood in terms of stabilization caused by spin-coupling augmented by dispersion, polarization, and charge transfer in competition with destabilizing Pauli repulsions. The EDA reveals distinguishing features of chemical bonds ranging across nonpolar, polar, ionic, and charge-shift bonds. The effect of electron correlation is assessed by comparison with Hartree-Fock results. Substituent effects are illustrated by comparing the C-C bond in ethane against that in bis(diamantane), and dispersion stabilization in the latter is quantified. Finally, three metal-metal bonds in experimentally characterized compounds are examined: a [Formula: see text]-[Formula: see text] dimer, the [Formula: see text]-[Formula: see text] bond in dizincocene, and the Mn-Mn bond in dimanganese decacarbonyl.

  19. Quantification of Hydrogen Bond Strength Based on Interaction Coordinates: A New Approach.

    Science.gov (United States)

    Pandey, Sarvesh Kumar; Manogaran, Dhivya; Manogaran, Sadasivam; Schaefer, Henry F

    2017-08-17

    A new approach to quantify hydrogen bond strengths based on interaction coordinates (HBSBIC) is proposed and is very promising. In this research, it is assumed that the projected force field of the fictitious three atoms fragment (DHA) where D is the proton donor and A is the proton acceptor from the full molecular force field of the H-bonded complex characterizes the hydrogen bond. The "interaction coordinate (IC)" derived from the internal compliance matrix elements of this three-atom fragment measures how the DH covalent bond (its electron density) responds to constrained optimization when the HA hydrogen bond is stretched by a known amount (its electron density is perturbed by a specified amount). This response of the DH bond, based on how the IC depends on the electron density along the HA bond, is a measure of the hydrogen bond strength. The inter- and intramolecular hydrogen bond strengths for a variety of chemical and biological systems are reported. When defined and evaluated using the IC approach, the HBSBIC index leads to satisfactory results. Because this involves only a three-atom fragment for each hydrogen bond, the approach should open up new directions in the study of "appropriate small fragments" in large biomolecules.

  20. Density functional theory, natural bond orbital and quantum theory of ...

    Indian Academy of Sciences (India)

    The sign of Hb depends on which contribution, potential or kinetic, will locally prevail on the BCP. The Lapla- cian is negative if the modulus of the potential energy outweighs two times the kinetic energy, which implies the covalent character of interaction, and it may con- cern covalent bonds as well as very strong H-bonds.

  1. Incorporation of in-plane interconnects to reflow bonding for electrical functionality

    International Nuclear Information System (INIS)

    Moğulkoç, B; Jansen, H V; Ter Brake, H J M; Elwenspoek, M C

    2011-01-01

    Incorporation of in-plane electrical interconnects to reflow bonding is studied to provide electrical functionality to lab-on-a-chip or microfluidic devices. Reflow bonding is the packaging technology, in which glass tubes are joined to silicon substrates at elevated temperatures. The tubes are used to interface the silicon-based fluidic devices and are directly compatible with standard Swagelok® connectors. After the bonding, the electrically conductive lines will allow probing into the volume confined by the tube, where the fluidic device operates. Therefore methods for fabricating electrical interconnects that survive the bonding procedure at elevated temperature and do not alter the properties of the bond interface are investigated

  2. Density functional theory, natural bond orbital and quantum theory of ...

    Indian Academy of Sciences (India)

    other words, there exists a certain cooperative effects between the intramolecular O1H1T ···N1T H-bond and intermolecular H-bonds in these complexes (TW1,. TW2 and TW3). There are structural evidences for such cooperativity. The positive RX−H values of the. Table 4. The second-perturbation energies E(2) (in kcal·mol.

  3. Metal-Free Approaches to Sterically-Hindered Bonds

    Science.gov (United States)

    Dunham, Veronica Vin-yi

    Developing methods to perform cross coupling reactions by means of catalysis is highly desirable in chemistry. Many industries in today's society, such as the petroleum, agriculture, pharmaceutical, electronics, and polymer industry, use catalysis to some extent whether it is to make molecules that offer crop protection or toward the synthesis of the active ingredient of a medication. It is noteworthy that over 90% of chemicals are made through catalytic processes and that the catalyst market reached $17 billion in 2014, which demonstrates the demand for such methods. While transition metal catalysts have advantages such as low catalyst loading, broad reactivity, and that they have been well studied, some disadvantages are that they can be relatively expensive and sometimes air sensitive which can make them challenging to use. Organocatalysis, specifically noncovalent catalysis operating through hydrogen bond donating interactions, offers an environmentally-friendly alternative to transition metal catalysis. Our lab utilizes organocatalysis as a strategy to synthesize challenging, sterically-hindered bonds. Nitrimines have been identified as powerful coupling partners for the sustainable construction of new sterically congested carbon-carbon and carbon-heteroatom bonds. Using urea catalysis, a metal-free method to synthesize previously inaccessible enamines has been developed. Conventional routes to synthesize enamines as important building blocks toward target molecules generally require Lewis/Bronsted acids or expensive transition metals; however, these methods are often unsuccessful when stericallyhindered substrates are used. To address this synthetic challenge, it was hypothesized that hydrogen bonding interactions between a urea organocatalyst and nitrimine would generate a reactive species suited for the effective carbon-nitrogen coupling with amines to give the desired enamine products. This reaction provides high yields (up to 99%) of enamines using a

  4. Infill architecture: Design approaches for in-between buildings and 'bond' as integrative element

    Directory of Open Access Journals (Sweden)

    Alfirević Đorđe

    2015-01-01

    Full Text Available The aim of the paper is to draw attention to the view that the two key elements in achieving good quality of architecture infill in immediate, current surroundings, are the selection of optimal creative method of infill architecture and adequate application of 'the bond' as integrative element, The success of achievement and the quality of architectural infill mainly depend on the assessment of various circumstances, but also on the professionalism, creativity, sensibility, and finally innovativeness of the architect, In order for the infill procedure to be carried out adequately, it is necessary to carry out the assessment of quality of the current surroundings that the object will be integrated into, and then to choose the creative approach that will allow the object to establish an optimal dialogue with its surroundings, On a wider scale, both theory and the practice differentiate thee main creative approaches to infill objects: amimetic approach (mimesis, bassociative approach and ccontrasting approach, Which of the stated approaches will be chosen depends primarily on the fact whether the existing physical structure into which the object is being infilled is 'distinct', 'specific' or 'indistinct', but it also depends on the inclination of the designer, 'The bond' is a term which in architecture denotes an element or zone of one object, but in some instances it can refer to the whole object which has been articulated in a specific way, with an aim of reaching the solution for the visual conflict as is often the case in situations when there is a clash between the existing objects and the newly designed or reconstructed object, This paper provides in-depth analysis of different types of bonds, such as 'direction as bond', 'cornice as bond', 'structure as bond', 'texture as bond' and 'material as bond', which indicate complexity and multiple layers of the designing process of object interpolation.

  5. Integrated reclamation: Approaching ecological function?

    Science.gov (United States)

    Ann L. Hild; Nancy L. Shaw; Ginger B. Paige

    2009-01-01

    Attempts to reclaim arid and semiarid lands have traditionally targeted plant species composition. Much research attention has been directed to seeding rates, species mixes and timing of seeding. However, in order to attain functioning systems, attention to structure and process must compliment existing efforts. We ask how to use a systems approach to enhance...

  6. Effective scheme for partitioning covalent bonds in density-functional embedding theory: From molecules to extended covalent systems.

    Science.gov (United States)

    Huang, Chen; Muñoz-García, Ana Belén; Pavone, Michele

    2016-12-28

    Density-functional embedding theory provides a general way to perform multi-physics quantum mechanics simulations of large-scale materials by dividing the total system's electron density into a cluster's density and its environment's density. It is then possible to compute the accurate local electronic structures and energetics of the embedded cluster with high-level methods, meanwhile retaining a low-level description of the environment. The prerequisite step in the density-functional embedding theory is the cluster definition. In covalent systems, cutting across the covalent bonds that connect the cluster and its environment leads to dangling bonds (unpaired electrons). These represent a major obstacle for the application of density-functional embedding theory to study extended covalent systems. In this work, we developed a simple scheme to define the cluster in covalent systems. Instead of cutting covalent bonds, we directly split the boundary atoms for maintaining the valency of the cluster. With this new covalent embedding scheme, we compute the dehydrogenation energies of several different molecules, as well as the binding energy of a cobalt atom on graphene. Well localized cluster densities are observed, which can facilitate the use of localized basis sets in high-level calculations. The results are found to converge faster with the embedding method than the other multi-physics approach ONIOM. This work paves the way to perform the density-functional embedding simulations of heterogeneous systems in which different types of chemical bonds are present.

  7. C(sp3)-H Bond Functionalization of Benzo[c]oxepines via C-O bond Cleavage: Formal [3+3] Synthesis of Multisubstituted Chromans.

    Science.gov (United States)

    Wang, Miao; Tang, Bo-Cheng; Xiang, Jia-Chen; Cheng, Yan; Wang, Zi-Xuan; Ma, Jin-Tian; Wu, Yan-Dong; Wu, An-Xin

    2018-03-01

    An efficient base-promoted C(sp 3 )-H bond functionalization strategy for the synthesis of multisubstituted chromans from the formal [3+3] cycloaddition of benzo[c]oxepines and electron-rich phenols has been developed. The corresponding 4H-chromenes can be easily obtained in excellent yields by simple filtration from chromans. Preliminary mechanistic studies indicate that the C-O bond cleavage is the key step for the C(sp 3 )-H bond functionalization and that this reaction could have occurred through tandem C-O bond cleavage/Michael addition/annulation reactions.

  8. Multiple hydrogen bond interactions in the processing of functionalized multi-walled carbon nanotubes.

    Science.gov (United States)

    Quintana, Mildred; Traboulsi, Hassan; Llanes-Pallas, Anna; Marega, Riccardo; Bonifazi, Davide; Prato, Maurizio

    2012-01-24

    In a set of unprecedented experiments combining "bottom-up" and "top-down" approaches, we report the engineering of patterned surfaces in which functionalized MWCNTs have been selectively adsorbed on polymeric matrices as obtained by microlithographic photo-cross-linking of polystyrene polymers bearing 2,6-di(acetylamino)-4-pyridyl moieties (PS1) deposited on glass or Si. All patterned surfaces have been characterized by optical, fluorescence, and SEM imaging techniques, showing the local confinement of the CNTs materials on the polymeric microgrids. These results open new possibilities toward the controlled manipulation of CNTs on surfaces, using H-bonding self-assembly as the main driving force. © 2011 American Chemical Society

  9. Novel electrochemical approach to study corrosion mechanism of Al-Au wire-bond pad interconnections

    DEFF Research Database (Denmark)

    Elisseeva, O. V.; Bruhn, A.; Cerezo, J.

    2013-01-01

    A gold-aluminium material combination is typically employed as an interconnection for microelectronic devices. One of the reliability risks of such devices is that of corrosion of aluminium bond pads resulting from the galvanic coupling between an aluminium bond pad and a gold wire. The research...... presented in this manuscript focuses on studying bond pad corrosion by selecting an appropriate model system and a dedicated set of electrochemical and analytical experimental tools. Taking into account the complex three-dimensional structure and the small dimensions of Au-Al interconnections (around 50......-100 μm), a dedicated and novel experimental approach was developed. Au-Al covered silicon chips were developed under clean room conditions. Three-dimensional electrodes were mimicked as flat, two-dimensional bond pad model systems, allowing the use of microelectrochemical local probe techniques. Thin...

  10. Radiological emergency response - a functional approach

    International Nuclear Information System (INIS)

    Chowdhury, P.

    1998-01-01

    The state of Louisiana's radiological emergency response programme is based on the federal guidance 'Criteria for Preparation and Evaluation of Radiological Emergency Response Plans and Preparedness in Support of Nuclear Power Plants' (NUREG-0654, FEMA-REP-1 Rev. 1). Over the past 14 years, the planning and implementation of response capabilities became more organized and efficient; the training programme has strengthened considerably; co-ordination with all participating agencies has assumed a more co-operative role, and as a result, a fairly well integrated response planning has evolved. Recently, a more 'functional' approach is being adopted to maximize the programme's efficiency not only for nuclear power plant emergency response, but radiological emergency response as a whole. First, several broad-based 'components' are identified; clusters of 'nodes' are generated for each component; these 'nodes' may be divided into 'sub-nodes' which will contain some 'attributes'; 'relational bonds' among the 'attributes' will exist. When executed, the process begins and continues with the 'nodes' assuming a functional and dynamic role based on the nature and characteristics of the 'attributes'. The typical response based on stand-alone elements is thus eliminated, the overlapping of functions is avoided, and a well structured and efficient organization is produced, that is essential for today's complex nature of emergency response. (author)

  11. Demonstration of Subscale Cermet Fuel Specimen Fabrication Approach Using Spark Plasma Sintering and Diffusion Bonding

    Science.gov (United States)

    Barnes, Marvin W.; Tucker, Dennis S.; Benensky, Kelsa M.

    2018-01-01

    Nuclear thermal propulsion (NTP) has the potential to expand the limits of human space exploration by enabling crewed missions to Mars and beyond. The viability of NTP hinges on the development of a robust nuclear fuel material that can perform in the harsh operating environment (> or = 2500K, reactive hydrogen) of a nuclear thermal rocket (NTR) engine. Efforts are ongoing to develop fuel material and to assemble fuel elements that will be stable during the service life of an NTR. Ceramic-metal (cermet) fuels are being actively pursued by NASA Marshall Space Flight Center (MSFC) due to their demonstrated high-temperature stability and hydrogen compatibility. Building on past cermet fuel development research, experiments were conducted to investigate a modern fabrication approach for cermet fuel elements. The experiments used consolidated tungsten (W)-60vol%zirconia (ZrO2) compacts that were formed via spark plasma sintering (SPS). The consolidated compacts were stacked and diffusion bonded to assess the integrity of the bond lines and internal cooling channel cladding. The assessment included hot hydrogen testing of the manufactured surrogate fuel and pure W for 45 minutes at 2500 K in the compact fuel element environmental test (CFEET) system. Performance of bonded W-ZrO2 rods was compared to bonded pure W rods to access bond line integrity and composite stability. Bonded surrogate fuels retained structural integrity throughout testing and incurred minimal mass loss.

  12. A density functional theory study on the hydrogen bonding interactions between luteolin and ethanol.

    Science.gov (United States)

    Zheng, Yan-Zhen; Xu, Jing; Liang, Qin; Chen, Da-Fu; Guo, Rui; Fu, Zhong-Min

    2017-08-01

    Ethanol is one of the most commonly used solvents to extract flavonoids from propolis. Hydrogen bonding interactions play an important role in the properties of liquid system. The main objective of the work is to study the hydrogen bonding interactions between flavonoid and ethanol. Luteolin is a very common flavonoid that has been found in different geographical and botanical propolis. In this work, it was selected as the representative flavonoid to do detailed research. The study was performed from a theoretical perspective using density functional theory (DFT) method. After careful optimization, there exist nine optimized geometries for the luteolin - CH 3 CH 2 OH complex. The binding distance of X - H···O, and the bond length, vibrational frequency, and electron density changes of X - H all indicate the formation of the hydrogen bond in the optimized geometries. In the optimized geometries, it is found that: (1) except for the H2', H5', and H6', CH 3 CH 2 OH has formed hydrogen bonds with all the hydrogen and oxygen atoms in luteolin. The hydrogen atoms in the hydroxyl groups of luteolin form the strongest hydrogen bonds with CH 3 CH 2 OH; (2) all of the hydrogen bonds are closed-shell interactions; (3) the strongest hydrogen bond is the O3' - H3'···O in structure A, while the weakest one is the C3 - H3···O in structure E; (4) the hydrogen bonds of O3' - H3'···O, O - H···O4, O - H···O3' and O - H···O7 are medium strength and covalent dominant in nature. While the other hydrogen bonds are weak strength and possess a dominant character of the electrostatic interactions in nature.

  13. Distinct roles of a tyrosine-associated hydrogen-bond network in fine-tuning the structure and function of heme proteins: two cases designed for myoglobin.

    Science.gov (United States)

    Liao, Fei; Yuan, Hong; Du, Ke-Jie; You, Yong; Gao, Shu-Qin; Wen, Ge-Bo; Lin, Ying-Wu; Tan, Xiangshi

    2016-10-20

    A hydrogen-bond (H-bond) network, specifically a Tyr-associated H-bond network, plays key roles in regulating the structure and function of proteins, as exemplified by abundant heme proteins in nature. To explore an approach for fine-tuning the structure and function of artificial heme proteins, we herein used myoglobin (Mb) as a model protein and introduced a Tyr residue in the secondary sphere of the heme active site at two different positions (107 and 138). We performed X-ray crystallography, UV-Vis spectroscopy, stopped-flow kinetics, and electron paramagnetic resonance (EPR) studies for the two single mutants, I107Y Mb and F138Y Mb, and compared to that of wild-type Mb under the same conditions. The results showed that both Tyr107 and Tyr138 form a distinct H-bond network involving water molecules and neighboring residues, which fine-tunes ligand binding to the heme iron and enhances the protein stability, respectively. Moreover, the Tyr107-associated H-bond network was shown to fine-tune both H2O2 binding and activation. With two cases demonstrated for Mb, this study suggests that the Tyr-associated H-bond network has distinct roles in regulating the protein structure, properties and functions, depending on its location in the protein scaffold. Therefore, it is possible to design a Tyr-associated H-bond network in general to create other artificial heme proteins with improved properties and functions.

  14. The significance of disulfide bonding in biological activity of HB-EGF, a mutagenesis approach

    OpenAIRE

    Hoskins, J.T.; Zhou, Z.; Harding, P.A.

    2008-01-01

    A site-directed mutagenesis approach was taken to disrupt each of 3 disulfide bonds within human HB-EGF by substituting serine for both cysteine residues that contribute to disulfide bonding. Each HB-EGF disulfide analogue (HB-EGF-Cys/Ser108/121, HB-EGF-Cys/Ser116/132, and HB-EGF-Cys/Ser134/143) was cloned under the regulation of the mouse metallothionein (MT) promoter and stably expressed in mouse fibroblasts. HB-EGF immunoreactive proteins with Mr of 6.5, 21 and 24kDa were observed from lys...

  15. A simple approach for immobilization of gold nanoparticles on graphene oxide sheets by covalent bonding

    NARCIS (Netherlands)

    Pham, Tuan Anh; Choi, Byung Choon; Lim, Kwon Taek; Jeong, Yeon Tae

    2011-01-01

    Amino - functionalized gold nanoparticles with a diameter of around 5 nm were immobilized onto the surface of graphene oxide sheets (GOS) by covalent bonding through a simple amidation reaction. Pristine graphite was firstly oxidized and exfoliated to obtain GOS, which further were acylated with

  16. Bond energy decomposition analysis for subsystem density functional theory

    NARCIS (Netherlands)

    Beyhan, S.M.; Gotz, A.W.; Visscher, L.

    2013-01-01

    We employed an explicit expression for the dispersion (D) energy in conjunction with Kohn-Sham (KS) density functional theory and frozen-density embedding (FDE) to calculate interaction energies between DNA base pairs and a selected set of amino acid pairs in the hydrophobic core of a small protein

  17. A Unified Bond Graph Modeling Approach for the Ejection Phase of the Cardiovascular System

    Directory of Open Access Journals (Sweden)

    LUBNA MOIN

    2016-07-01

    Full Text Available In this paper the unified Bond Graph model of the left ventricle ejection phase is presented, simulated and validated. The integro-differential and ordinary differential equations obtained from the bond graph models are simulated using ODE45 (Ordinary Differential Equation Solver on MATLAB and Simulink. The results, thus, obtained are compared with CVS (Cardiovascular System physiological data present in Simbiosys (a software for simulating biological systems and also with the CVS Wiggers diagram of heart cycle. As the cardiac activity is a multi domain process that includes mechanical, hydraulic, chemical and electrical events; therefore, for modeling such systems a unified modeling approach is needed. In this paper the unified Bond Graph model of the left ventricle ejection phase is proposed. The Bond Graph conventionalism approach is a graphical method principally powerful to portray multi-energy systems, as it is formulated on the portrayal of power exchanges. The model takes into account a simplified description of the left ventricle which is close to the medical investigation promoting the apperception and the dialogue between engineers and physiologists.

  18. Nonorthogonal orbital based N-body reduced density matrices and their applications to valence bond theory. I. Hamiltonian matrix elements between internally contracted excited valence bond wave functions

    Science.gov (United States)

    Chen, Zhenhua; Chen, Xun; Wu, Wei

    2013-04-01

    In this series, the n-body reduced density matrix (n-RDM) approach for nonorthogonal orbitals and their applications to ab initio valence bond (VB) methods are presented. As the first paper of this series, Hamiltonian matrix elements between internally contracted VB wave functions are explicitly provided by means of nonorthogonal orbital based RDM approach. To this end, a more generalized Wick's theorem, called enhanced Wick's theorem, is presented both in arithmetical and in graphical forms, by which the deduction of expressions for the matrix elements between internally contracted VB wave functions is dramatically simplified, and the matrix elements are finally expressed in terms of tensor contractions of electronic integrals and n-RDMs of the reference VB self-consistent field wave function. A string-based algorithm is developed for the purpose of evaluating n-RDMs in an efficient way. Using the techniques presented in this paper, one is able to develop new methods and efficient algorithms for nonorthogonal orbital based many-electron theory much easier than by use of the first quantized formulism.

  19. Longitudinal associations between parental bonding, parenting stress, and executive functioning in toddlerhood

    OpenAIRE

    De Cock, E.S.A.; Henrichs, J.; Klimstra, T.A.; Maas, A.J.B.M.; Vreeswijk, C.M.J.M.; Meeus, W.H.J.; Van Bakel, H.J.A.

    2017-01-01

    Early executive functioning is an important predictor for future development of children’s cognitive skills and behavioral outcomes. Parenting behavior has proven to be a key environmental determinant of child executive functioning. However, the association of parental affect and cognitions directed to the child with child executive functioning has been understudied. Therefore, in the present study we examine the associations between parental bonding (i.e., the affective tie from parent to ch...

  20. A general approach to intermolecular carbonylation of arene C-H bonds to ketones through catalytic aroyl triflate formation

    Science.gov (United States)

    Garrison Kinney, R.; Tjutrins, Jevgenijs; Torres, Gerardo M.; Liu, Nina Jiabao; Kulkarni, Omkar; Arndtsen, Bruce A.

    2018-02-01

    The development of metal-catalysed methods to functionalize inert C-H bonds has become a dominant research theme in the past decade as an approach to efficient synthesis. However, the incorporation of carbon monoxide into such reactions to form valuable ketones has to date proved a challenge, despite its potential as a straightforward and green alternative to Friedel-Crafts reactions. Here we describe a new approach to palladium-catalysed C-H bond functionalization in which carbon monoxide is used to drive the generation of high-energy electrophiles. This offers a method to couple the useful features of metal-catalysed C-H functionalization (stable and available reagents) and electrophilic acylations (broad scope and selectivity), and synthesize ketones simply from aryl iodides, CO and arenes. Notably, the reaction proceeds in an intermolecular fashion, without directing groups and at very low palladium-catalyst loadings. Mechanistic studies show that the reaction proceeds through the catalytic build-up of potent aroyl triflate electrophiles.

  1. Functionalized olefin cross-coupling to construct carbon-carbon bonds

    Science.gov (United States)

    Lo, Julian C.; Gui, Jinghan; Yabe, Yuki; Pan, Chung-Mao; Baran, Phil S.

    2014-12-01

    Carbon-carbon (C-C) bonds form the backbone of many important molecules, including polymers, dyes and pharmaceutical agents. The development of new methods to create these essential connections in a rapid and practical fashion has been the focus of numerous organic chemists. This endeavour relies heavily on the ability to form C-C bonds in the presence of sensitive functional groups and congested structural environments. Here we report a chemical transformation that allows the facile construction of highly substituted and uniquely functionalized C-C bonds. Using a simple iron catalyst, an inexpensive silane and a benign solvent under ambient atmosphere, heteroatom-substituted olefins are easily reacted with electron-deficient olefins to create molecular architectures that were previously difficult or impossible to access. More than 60 examples are presented with a wide array of substrates, demonstrating the chemoselectivity and mildness of this simple reaction.

  2. A density functional theory for colloids with two multiple bonding associating sites.

    Science.gov (United States)

    Haghmoradi, Amin; Wang, Le; Chapman, Walter G

    2016-06-22

    Wertheim's multi-density formalism is extended for patchy colloidal fluids with two multiple bonding patches. The theory is developed as a density functional theory to predict the properties of an associating inhomogeneous fluid. The equation of state developed for this fluid depends on the size of the patch, and includes formation of cyclic, branched and linear clusters of associated species. The theory predicts the density profile and the fractions of colloids in different bonding states versus the distance from one wall as a function of bulk density and temperature. The predictions from our theory are compared with previous results for a confined fluid with four single bonding association sites. Also, comparison between the present theory and Monte Carlo simulation indicates a good agreement.

  3. Regioselective oxidative trifluoromethylation of imidazoheterocycles via C(sp2)-H bond functionalization.

    Science.gov (United States)

    Monir, Kamarul; Bagdi, Avik Kumar; Ghosh, Monoranjan; Hajra, Alakananda

    2015-02-06

    Catalytic oxidative trifluoromethylation of imidazopyridines has been carried out at room temperature through the functionalization of the sp(2) C-H bond employing Langlois reagent under ambient air. A library of 3-(trifluoromethyl)imidazo[1,2-a]pyridines with broad functionalities have been synthesized regioselectively. This methodology is also applicable to imidazo[2,1-b]thiazole and benzo[d]imidazo[2,1-b]thiazole.

  4. Family Functioning and Parental Bonding During Childhood in Adults Diagnosed With ADHD.

    Science.gov (United States)

    Montejo, José E; Durán, Mariona; Del Mar Martínez, María; Hilari, Ainoa; Roncalli, Nicoletta; Vilaregut, Anna; Corrales, Montserrat; Nogueira, Mariana; Casas, Miguel; Linares, Juan Luis; Ramos-Quiroga, J Antoni

    2015-08-24

    This work assesses family functioning, parental bonding, and the relationship between the two in adults diagnosed with ADHD. The study used a retrospective, ex post facto design and consisted of 100 adult participants, who were distributed into two groups: with and without diagnosis of ADHD. Two family assessment instruments were applied: the Family Adaptability and Cohesion Evaluation Scale short spanish version (FACES-20esp)) and the Parental Bonding Instrument (PBI). The diagnosis of ADHD was done by using a semistructured interview for Diagnostic and Statistical Manual of Mental Disorders (4th ed.; DSM-IV) criteria (Conners' Adult ADHD Diagnostic Interview for DSM-IV [CAADID]). The results showed that higher rigidity and lower emotional connection were significantly associated with ADHD family functioning. Regarding parental bonding, the results showed significant differences only in the care dimension, with the ADHD group reporting lower care than the control group. The results suggest that ADHD families present dysfunctional family functioning with a rigid, separated typology, and parental bonding based on control without affection. © 2015 SAGE Publications.

  5. Atom probe tomography simulations and density functional theory calculations of bonding energies in Cu3Au

    KAUST Repository

    Boll, Torben

    2012-10-01

    In this article the Cu-Au binding energy in Cu3Au is determined by comparing experimental atom probe tomography (APT) results to simulations. The resulting bonding energy is supported by density functional theory calculations. The APT simulations are based on the Müller-Schottky equation, which is modified to include different atomic neighborhoods and their characteristic bonds. The local environment is considered up to the fifth next nearest neighbors. To compare the experimental with simulated APT data, the AtomVicinity algorithm, which provides statistical information about the positions of the neighboring atoms, is applied. The quality of this information is influenced by the field evaporation behavior of the different species, which is connected to the bonding energies. © Microscopy Society of America 2012.

  6. The hydrogen bond in ice probed by soft x-ray spectroscopy and density functional theory

    International Nuclear Information System (INIS)

    Nilsson, A.; Ogasawara, H.; Cavalleri, M.; Nordlund, D.; Nyberg, M.; Wernet, Ph.; Pettersson, L.G.M.

    2005-01-01

    We combine photoelectron and x-ray absorption spectroscopy with density functional theory to derive a molecular orbital picture of the hydrogen bond in ice. We find that the hydrogen bond involves donation and back-donation of charge between the oxygen lone pair and the O-H antibonding orbitals on neighboring molecules. Together with internal s-p rehybridization this minimizes the repulsive charge overlap of the connecting oxygen and hydrogen atoms, which is essential for a strong attractive electrostatic interaction. Our joint experimental and theoretical results demonstrate that an electrostatic model based on only charge induction from the surrounding medium fails to properly describe the internal charge redistributions upon hydrogen bonding

  7. Chemical bond fundamental aspects of chemical bonding

    CERN Document Server

    Frenking, Gernot

    2014-01-01

    This is the perfect complement to ""Chemical Bonding - Across the Periodic Table"" by the same editors, who are two of the top scientists working on this topic, each with extensive experience and important connections within the community. The resulting book is a unique overview of the different approaches used for describing a chemical bond, including molecular-orbital based, valence-bond based, ELF, AIM and density-functional based methods. It takes into account the many developments that have taken place in the field over the past few decades due to the rapid advances in quantum chemica

  8. Developing a New Teaching Approach for the Chemical Bonding Concept Aligned with Current Scientific and Pedagogical Knowledge

    Science.gov (United States)

    Nahum, Tami Levy; Mamlok-Naaman, Rachel; Hofstein, Avi; Krajcik, Joseph

    2007-01-01

    The traditional pedagogical approach for teaching chemical bonding is often overly simplistic and not aligned with the most up-to-date scientific models. As a result, high-school students around the world lack fundamental understanding of chemical bonding. In order to improve students' understanding of this concept, it was essential to propose a…

  9. Nonlinear Dynamic Analysis of RC Shear Walls using Damage Mechanics Approach Considering Bond-Slip Effects

    Directory of Open Access Journals (Sweden)

    N. Davoodi

    2015-07-01

    Full Text Available In this research, nonlinear dynamic analysis of concrete shear wall using a new nonlinear model based on damage mechanics approach and considering bond slip effects is presented. Nonlinear behavior of concrete is modeled by a rotational smeared crack model using damage mechanics approach. The proposed model considers major characteristics of the concrete subjected to two and three dimensional loading conditions. These characteristics are pre-softening behavior, softening initiation criteria and fracture energy conservation. The model was used in current research analysis after verification by some available numerical tests. Reinforcements are modeled by a bilinear relationship using two models: Discrete truss steel element and Smeared model. In Discrete model the effects of bond-slide between concrete and rebar is mentioned using the bond-link element model concept. Based on the presented algorithms and methodology, an FEM code is developed in FORTRAN. The validity of the proposed models and numerical algorithms has been checked using the available experimental results. Finally, numerical simulation of CAMUS I and CAMUS III reinforced concrete shear walls is carried out. Comparisons of deduced results confirm the validity of proposed models. The obtained results, both in the expected displacements and crack profiles for the walls, show a good accuracy with respect to the experimental results. Also, using discrete truss element model with respect to the smeared steel model leads to increasing the accuracy of maximum displacement response to 7% in analysis.

  10. Diagnostic Approach to Functional Recovery

    DEFF Research Database (Denmark)

    Havsteen, Inger; Madsen, Kristoffer H; Christensen, Hanne Krarup

    2013-01-01

    available and does not pose any adverse effects, repeated fMRI measurements provide unprecedented possibilities to prospectively assess the time course of reorganization in functional neural networks after stroke and relate the temporospatial dynamics of reorganization at the systems level to functional...

  11. Push-out bond strength and SEM evaluation of a new bonding approach into the root canal

    Directory of Open Access Journals (Sweden)

    Carlos Augusto Carvalho

    2012-12-01

    Full Text Available OBJECTIVE: This study evaluated the performance of different adhesive systems in fiber post placement aiming to clarify the influence of different hydrophobic experimental blend adhesives, and of one commercially available adhesive on the frictional retention during a luting procedure. MATERIAL AND METHODS: One luting agent (70 Wt% BisGMA, 28.5% TEGDMA; 1.5% p-tolyldiethanolamine to cement fiber posts into root canals was applied with 4 different adhesive combinations: Group 1: The etched roots were rinsed with water for 30 s to remove the phosphoric acid, then rinsed with 99.6% ethanol for 30 s, and blotdried. A trial adhesive (base to catalyst on a 1:1 ratio was used with an experimental luting agent (35% Bis-GMA, 14.37% TeGDMA, 0.5% eDMAB, 0.13% CQ; Group 2: A trial adhesive (base to catalyst on a 1:2 ratio was luted as in Group 1; Group 3: One-Step Plus (OSP, Bisco Inc. following the ethanol bonding technique in combination with the luting agent as in Group 1; Group 4: OSP strictly following the manufacturer's instructions using the luting agent as in Group 1. The groups were challenged with push-out tests. Posted root slices were loaded until post segment extrusion in the apical-coronal direction. Failure modes were analyzed under scanning electron microscopy. RESULTS: Push-out strength was not significantly influenced by the luting agent (p>0.05. No statistically significant differences among the tested groups were found as Group 1 (exp 1 - ethanol-wet bonding technique=Group 2 (exp 2 - ethanol-wet bonding technique=Group 3 (OSP - ethanol-wet bonding technique=Group 4 (control, OSP - water-wet bonding technique (p>0.05. The dominating failure modes in all the groups were cohesive/adhesive failures, which were predominantly observed on the post/luting agent interface. CONCLUSIONS: The results of this study support the hypothesis that the proposal to replace water with ethanol to bond fiber posts to the root canal using highly hydrophobic

  12. The trouble with chemical energy: why understanding bond energies requires an interdisciplinary systems approach.

    Science.gov (United States)

    Cooper, Melanie M; Klymkowsky, Michael W

    2013-06-01

    Helping students understand "chemical energy" is notoriously difficult. Many hold inconsistent ideas about what energy is, how and why it changes during the course of a chemical reaction, and how these changes are related to bond energies and reaction dynamics. There are (at least) three major sources for this problem: 1) the way biologists talk about chemical energy (which is also the way we talk about energy in everyday life); 2) the macroscopic approach to energy concepts that is common in physics and physical sciences; and 3) the failure of chemistry courses to explicitly link molecular with macroscopic energy ideas. From a constructivist perspective, it is unlikely that students can, without a coherent understanding of such a central concept, attain a robust and accurate understanding of new concepts. However, changes are on the horizon, guided by the increasing understanding that difficult concepts require coherent, well-designed learning progressions and the new National Research Council Framework for K-12 Science Education. We provide supporting evidence for our assertions and suggestions for an interdisciplinary learning progression designed to better approach the concept of bond energies, a first step in an understanding chemical energy and behavior of reaction systems that is central to biological systems.

  13. Bond centred functions in relativistic and non-relativistic calculations for diatomics

    International Nuclear Information System (INIS)

    Matito, Eduard; Kobus, Jacek; Styszynski, Jacek

    2006-01-01

    In this paper, we discuss the performance of molecular basis sets consisting of atomic centred (AC) functions augmented with bond centred (BC) functions in relativistic and non-relativistic calculations carried out at the Hartree-Fock and several correlated levels of approximation. While usually non-correlated calculations employing BC functions can be performed at a lower computational cost as compared with those making use of energy optimized AC basis sets, the correlated calculations are always more accurate and less expensive with the latter. It is demonstrated that both correlated or non-correlated calculations always benefit from the addition of a few BC functions with a moderate increase of computational effort. The performance of basis sets containing even-tempered BC functions is also studied and their usage is advocated in case of relativistic calculations

  14. Stressful parental bonding exaggerate the functional and emotional disturbances of primary dysmenorrhea

    Directory of Open Access Journals (Sweden)

    Kai Xu

    2014-12-01

    Full Text Available Background: Some evidence suggests that women with primary dysmenorrhea (or painful period often have traumatic experience with parental attachments, but the exact relationship between styles of the parental bonding and the detailed aspects of the disorder is unclear. Methods: From university-student women, we invited 50 primary dysmenorrhea patients and 111 healthy volunteers to undergo tests of the functional and emotional measure of dysmenorrhea (FEMD, the Family Relationship Questionnaire (FRQ, and the visual analog scale for the pain intensity experienced. Results: Besides the high scores of the FEMD functional and emotional scales, the dysmenorrhea patients also scored significantly higher than the healthy controls on the FRQ scales of paternal dominance and maternal abuse. In patients, the FEMD Emotional scale was negatively predicted by the Paternal Freedom Release scale and the FEMD functional scale was positively predicted by the Maternal Dominance scale. Conclusion: Inappropriate parental bonding or chronic traumatic attachment styles have respective relationships with the functional and emotional disturbances experienced by the primary dysmenorrhea patients.

  15. Nonequilibrium Green's functions approach to inhomogeneous systems

    CERN Document Server

    Balzer, Karsten

    2013-01-01

    This book offers a self-contained introduction to non-equilibrium quantum particle dynamics for inhomogeneous systems, including a survey of recent breakthroughs pioneered by the authors and others. The approach is based on real-time Green's functions.

  16. A Bond Graph Approach for the Modeling and Simulation of a Buck Converter

    Directory of Open Access Journals (Sweden)

    Rached Zrafi

    2018-01-01

    Full Text Available This paper deals with the modeling of bond graph buck converter systems. The bond graph formalism, which represents a heterogeneous formalism for physical modeling, is used to design a sub-model of a power MOSFET and PiN diode switchers. These bond graph models are based on the device’s electrical elements. The application of these models to a bond graph buck converter permit us to obtain an invariant causal structure when the switch devices change state. This paper shows the usefulness of the bond graph device’s modeling to simulate an implicit bond graph buck converter.

  17. The significance of disulfide bonding in biological activity of HB-EGF, a mutagenesis approach

    International Nuclear Information System (INIS)

    Hoskins, J.T.; Zhou, Z.; Harding, P.A.

    2008-01-01

    A site-directed mutagenesis approach was taken to disrupt each of 3 disulfide bonds within human HB-EGF by substituting serine for both cysteine residues that contribute to disulfide bonding. Each HB-EGF disulfide analogue (HB-EGF-Cys/Ser 108/121 , HB-EGF-Cys/Ser 116/132 , and HB-EGF-Cys/Ser 134/143 ) was cloned under the regulation of the mouse metallothionein (MT) promoter and stably expressed in mouse fibroblasts. HB-EGF immunoreactive proteins with M r of 6.5, 21 and 24 kDa were observed from lysates of HB-EGF and each HB-EGF disulfide analogue. HB-EGF immunohistochemical analyses of each HB-EGF stable cell line demonstrated ubiquitous protein expression except HB-EGF-Cys/Ser 108/121 and HB-EGF-Cys/Ser 116/132 stable cell lines which exhibited accumulated expression immediately outside the nucleus. rHB-EGF, HB-EGF, and HB-EGF 134/143 proteins competed with 125 I-EGF in an A431 competitive binding assay, whereas HB-EGF-Cys/Ser 108/121 and HB-EGF-Cys/Ser 116/132 failed to compete. Each HB-EGF disulfide analogue lacked the ability to stimulate tyrosine phosphorylation of the 170 kDa EGFR. These results suggest that HB-EGF-Cys/Ser 134/143 antagonizes EGFRs

  18. Towards a unified description of the hydrogen bond network of liquid water: A dynamics based approach

    International Nuclear Information System (INIS)

    Ozkanlar, Abdullah; Zhou, Tiecheng; Clark, Aurora E.

    2014-01-01

    The definition of a hydrogen bond (H-bond) is intimately related to the topological and dynamic properties of the hydrogen bond network within liquid water. The development of a universal H-bond definition for water is an active area of research as it would remove many ambiguities in the network properties that derive from the fixed definition employed to assign whether a water dimer is hydrogen bonded. This work investigates the impact that an electronic-structure based definition, an energetic, and a geometric definition of the H-bond has upon both topological and dynamic network behavior of simulated water. In each definition, the use of a cutoff (either geometric or energetic) to assign the presence of a H-bond leads to the formation of transiently bonded or broken dimers, which have been quantified within the simulation data. The relative concentration of transient species, and their duration, results in two of the three definitions sharing similarities in either topological or dynamic features (H-bond distribution, H-bond lifetime, etc.), however no two definitions exhibit similar behavior for both classes of network properties. In fact, two networks with similar local network topology (as indicated by similar average H-bonds) can have dramatically different global network topology (as indicated by the defect state distributions) and altered H-bond lifetimes. A dynamics based correction scheme is then used to remove artificially transient H-bonds and to repair artificially broken bonds within the network such that the corrected network exhibits the same structural and dynamic properties for two H-bond definitions (the properties of the third definition being significantly improved). The algorithm described represents a significant step forward in the development of a unified hydrogen bond network whose properties are independent of the original hydrogen bond definition that is employed

  19. Origins of Protons in C-H Bond Insertion Products of Phenols: Proton-Self-Sufficient Function via Water Molecules.

    Science.gov (United States)

    Luo, Zhoujie; Gao, Ya; Zhu, Tong; Zhang, John Zenghui; Xia, Fei

    2017-08-31

    Water molecules can serve as proton shuttles for proton transfer in the C-H bond insertion reactions catalyzed by transition metal complexes. Recently, the control experiments performed for C-H bond insertion of phenol and anisol by gold carbenes show that large discrepancy exists in the yields of hydrogenated and deuterated products. Thus, we conducted a detailed theoretical analysis on the function of water molecules in the C-H bond insertion reactions. The comparison of calculated results and control experiments indicates that the solution water molecules play a crucial role of proton shuttle in C-H bond insertion. In particular, it was found that the hydroxyl groups in phenols were capable of donating protons via water shuttles for the production of C-H products, which had a substantial influence on the yields of inserted products. The hydroxyl groups instead of C-H bonds in phenols function like "proton reservoirs" in the C-H bond insertion, which we call the "proton self-sufficient" (PSS) function of phenol. The PSS function of phenol indicates that the substrates with and without proton reservoirs will lead to different C-H bond insertion products.

  20. Understanding the bonding nature of uranyl ion and functionalized graphene: a theoretical study.

    Science.gov (United States)

    Wu, Qun-Yan; Lan, Jian-Hui; Wang, Cong-Zhi; Xiao, Cheng-Liang; Zhao, Yu-Liang; Wei, Yue-Zhou; Chai, Zhi-Fang; Shi, Wei-Qun

    2014-03-20

    Studying the bonding nature of uranyl ion and graphene oxide (GO) is very important for understanding the mechanism of the removal of uranium from radioactive wastewater with GO-based materials. We have optimized 22 complexes between uranyl ion and GO applying density functional theory (DFT) combined with quasi-relativistic small-core pseudopotentials. The studied oxygen-containing functional groups include hydroxyl, carboxyl, amido, and dimethylformamide. It is observed that the distances between uranium atoms and oxygen atoms of GO (U-OG) are shorter in the anionic GO complexes (uranyl/GO(-/2-)) compared to the neutral GO ones (uranyl/GO). The formation of hydrogen bonds in the uranyl/GO(-/2-) complexes can enhance the binding ability of anionic GO toward uranyl ions. Furthermore, the thermodynamic calculations show that the changes of the Gibbs free energies in solution are relatively more negative for complexation reactions concerning the hydroxyl and carboxyl functionalized anionic GO complexes. Therefore, both the geometries and thermodynamic energies indicate that the binding abilities of uranyl ions toward GO modified by hydroxyl and carboxyl groups are much stronger compared to those by amido and dimethylformamide groups. This study can provide insights for designing new nanomaterials that can efficiently remove radionuclides from radioactive wastewater.

  1. Functional integral approach to classical statistical dynamics

    International Nuclear Information System (INIS)

    Jensen, R.V.

    1980-04-01

    A functional integral method is developed for the statistical solution of nonlinear stochastic differential equations which arise in classical dynamics. The functional integral approach provides a very natural and elegant derivation of the statistical dynamical equations that have been derived using the operator formalism of Martin, Siggia, and Rose

  2. Functional integral approach to classical statistical dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, R.V.

    1980-04-01

    A functional integral method is developed for the statistical solution of nonlinear stochastic differential equations which arise in classical dynamics. The functional integral approach provides a very natural and elegant derivation of the statistical dynamical equations that have been derived using the operator formalism of Martin, Siggia, and Rose.

  3. Block-Localized Density Functional Theory (BLDFT), Diabatic Coupling, and Their Use in Valence Bond Theory for Representing Reactive Potential Energy Surfaces

    Science.gov (United States)

    Cembran, Alessandro; Song, Lingchun; Mo, Yirong; Gao, Jiali

    2010-01-01

    A multistate density functional theory in the framework of the valence bond model is described. The method is based on a block-localized density functional theory (BLDFT) for the construction of valence-bond-like diabatic electronic states and is suitable for the study of electron transfer reactions and for the representation of reactive potential energy surfaces. The method is equivalent to a valence bond theory with the treatment of the localized configurations by using density functional theory (VBDFT). In VBDFT, the electron densities and energies of the valence bond states are determined by BLDFT. A functional estimate of the off-diagonal matrix elements of the VB Hamiltonian is proposed, making use of the overlap integral between Kohn–Sham determinants and the exchange-correlation functional for the ground state substituted with the transition (exchange) density. In addition, we describe an approximate approach, in which the off-diagonal matrix element is computed by wave function theory using block-localized Kohn–Sham orbitals. The key feature is that the electron density of the adiabatic ground state is not directly computed nor used to obtain the ground-state energy; the energy is determined by diagonalization of the multistate valence bond Hamiltonian. This represents a departure from the standard single-determinant Kohn–Sham density functional theory. The multistate VBDFT method is illustrated by the bond dissociation of H2+ and a set of three nucleophilic substitution reactions in the DBH24 database. In the dissociation of H2+, the VBDFT method yields the correct asymptotic behavior as the two protons stretch to infinity, whereas approximate functionals fail badly. For the SN2 nucleophilic substitution reactions, the hybrid functional B3LYP severely underestimates the barrier heights, while the approximate two-state VBDFT method overcomes the self-interaction error, and overestimates the barrier heights. Inclusion of the ionic state in a three

  4. Substituent Effects on Hydrogen Bonds in DNA : A Kohn-Sham DFT Approach

    NARCIS (Netherlands)

    Guerra, Célia Fonseca; Bickelhaupt, F. Matthias

    2006-01-01

    In this Chapter, we discuss how the hydrogen bonds in Watson-Crick base pairs can be tuned both structurally and in terms of bond strength by exposing the DNA bases to different kinds of substitutions: (1) substitution in the X-H Y hydrogen bonding moiety, (2) remote substitution, i.e., introducing

  5. Density functional approaches to nuclear dynamics

    OpenAIRE

    Nakatsukasa, T.; Ebata, S.; Avogadro, P.; Guo, L.; Inakura, T.; Yoshida, K.

    2012-01-01

    We present background concepts of the nuclear density functional theory (DFT) and applications of the time-dependent DFT with the Skyrme energy functional for nuclear response functions. Practical methods for numerical applications of the time-dependent Hartree-Fock-Bogoliubov theory (TDHFB) are proposed; finite amplitude method and canonical-basis TDHFB. These approaches are briefly reviewed and some numerical applications are shown to demonstrate their feasibility.

  6. An inverse approach for elucidating dendritic function

    Directory of Open Access Journals (Sweden)

    Benjamin Torben-Nielsen

    2010-09-01

    Full Text Available We outline an inverse approach for investigating dendritic function-structure relationships by optimizing dendritic trees for a-priori chosen computational functions. The inverse approach can be applied in two different ways. First, we can use it as a `hypothesis generator' in which we optimize dendrites for a function of general interest. The optimization yields an artificial dendrite that is subsequently compared to real neurons. This comparison potentially allows us to propose hypotheses about the function of real neurons. In this way, we investigated dendrites that optimally perform input-order detection. Second, we can use it as a `function confirmation' by optimizing dendrites for functions hypothesized to be performed by classes of neurons. If the optimized, artificial, dendrites resemble the dendrites of real neurons the artificial dendrites corroborate the hypothesized function of the real neuron. Moreover, properties of the artificial dendrites can lead to predictions about yet unmeasured properties. In this way, we investigated wide-field motion integration performed by the VS cells of the fly visual system. In outlining the inverse approach and two applications, we also elaborate on the nature of dendritic function. We furthermore discuss the role of optimality in assigning functions to dendrites and point out interesting future directions.

  7. Parental Bonding

    Directory of Open Access Journals (Sweden)

    T. Paul de Cock

    2014-08-01

    Full Text Available Estimating the early parent–child bonding relationship can be valuable in research and practice. Retrospective dimensional measures of parental bonding provide a means for assessing the experience of the early parent–child relationship. However, combinations of dimensional scores may provide information that is not readily captured with a dimensional approach. This study was designed to assess the presence of homogeneous groups in the population with similar profiles on parental bonding dimensions. Using a short version of the Parental Bonding Instrument (PBI, three parental bonding dimensions (care, authoritarianism, and overprotection were used to assess the presence of unobserved groups in the population using latent profile analysis. The class solutions were regressed on 23 covariates (demographics, parental psychopathology, loss events, and childhood contextual factors to assess the validity of the class solution. The results indicated four distinct profiles of parental bonding for fathers as well as mothers. Parental bonding profiles were significantly associated with a broad range of covariates. This person-centered approach to parental bonding has broad utility in future research which takes into account the effect of parent–child bonding, especially with regard to “affectionless control” style parenting.

  8. Inferring modules of functionally interacting proteins using the Bond Energy Algorithm

    Directory of Open Access Journals (Sweden)

    Vallejo Edgar E

    2008-06-01

    Full Text Available Abstract Background Non-homology based methods such as phylogenetic profiles are effective for predicting functional relationships between proteins with no considerable sequence or structure similarity. Those methods rely heavily on traditional similarity metrics defined on pairs of phylogenetic patterns. Proteins do not exclusively interact in pairs as the final biological function of a protein in the cellular context is often hold by a group of proteins. In order to accurately infer modules of functionally interacting proteins, the consideration of not only direct but also indirect relationships is required. In this paper, we used the Bond Energy Algorithm (BEA to predict functionally related groups of proteins. With BEA we create clusters of phylogenetic profiles based on the associations of the surrounding elements of the analyzed data using a metric that considers linked relationships among elements in the data set. Results Using phylogenetic profiles obtained from the Cluster of Orthologous Groups of Proteins (COG database, we conducted a series of clustering experiments using BEA to predict (upper level relationships between profiles. We evaluated our results by comparing with COG's functional categories, And even more, with the experimentally determined functional relationships between proteins provided by the DIP and ECOCYC databases. Our results demonstrate that BEA is capable of predicting meaningful modules of functionally related proteins. BEA outperforms traditionally used clustering methods, such as k-means and hierarchical clustering by predicting functional relationships between proteins with higher accuracy. Conclusion This study shows that the linked relationships of phylogenetic profiles obtained by BEA is useful for detecting functional associations between profiles and extending functional modules not found by traditional methods. BEA is capable of detecting relationship among phylogenetic patterns by linking them through a

  9. Exclusive Aromatic vs Aliphatic C-H Bond Functionalization by Carbene Insertion with Gold-based Catalysts

    OpenAIRE

    Rivilla de la Cruz, Iván; Gómez Emeterio, Bella Pilar; Romero Fructos-Vázquez, Manuel; Díaz Requejo, María Mar; Pérez Romero, Pedro José

    2011-01-01

    The direct functionalization of aromatic C-H bonds by carbene insertion from diazocompounds catalyzed by gold complexes with N-heterocyclic ligands is described. The reaction is completely selective toward the Csp2-H bonds, other Csp3-H bonds remaining unreacted. A study with a several NHC ligands in Au(I) and Au(III) complexes has been performed. A potential application in profen derivatives has also been developed DGI (CTQ2008-00042BQU and Consolider Ingenio 2010, Grant CSD2006-0003) and...

  10. Thermodynamic functions of hydrogen bonding of amines in methanol derived from solution calorimetry data and headspace analysis

    International Nuclear Information System (INIS)

    Zaitseva, Ksenia V.; Varfolomeev, Mikhail A.; Solomonov, Boris N.

    2012-01-01

    Highlights: ► Solution enthalpies and activity coefficients of amines in methanol were measured. ► Thermodynamic functions of H-bonding of amines with methanol were determined. ► Specific interaction entropy of amines in methanol can be about zero or positive. ► Cooperativity of H-bonds in methanol media is smaller than in water solutions. ► A new view on analysis of specific interaction of solute with methanol is presented. - Abstract: Reactivity and equilibrium properties of organic molecules in self-associated liquids greatly depend on the hydrogen bonding with solvent. This work contains comprehensive thermodynamic analysis of hydrogen bonding of aliphatic and aromatic amines in self-associated solvent methanol. Enthalpies of solution at infinite dilution and limiting activity coefficients for the studied systems were measured experimentally. Enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol were determined. These values were found to be decreased compared with hydrogen bond energy in equimolar complexes “methanol–amine” determined in inert solvent or base media. A linear dependence between enthalpies and Gibbs energies of hydrogen bonding of amines with neat methanol was observed. It was firstly revealed that the entropy of specific interactions of amines with neat methanol can be about zero or positive. Disruption of solvent–solvent hydrogen bonds can be regarded as the most important step during dissolution of amine in methanol. It was found that the cooperative effect influences on the Gibbs energies of hydrogen bonding of amines in methanol, but in a lesser extent than in aqueous solutions. The new results show that the hydrogen bonding process in the self-associated solvents differs significantly from equimolar complexation in aprotic media.

  11. Flexural and tensile bond strength, related via a stochastic numerical approach

    NARCIS (Netherlands)

    Pluijm, R. van der

    1998-01-01

    The flexural strength of masonry parallel to the bed joint depends on the geometry of the cross section, tensile bond strength, fracture energy, stiffness of units and of mortar joints. In experiments, tensile bond strength and fracture energy determined on relatively small specimens, show a large

  12. Covalent functionalization of graphene by azobenzene with molecular hydrogen bonds for long-term solar thermal storage.

    Science.gov (United States)

    Feng, Yiyu; Liu, Hongpo; Luo, Wen; Liu, Enzuo; Zhao, Naiqin; Yoshino, Katsumi; Feng, Wei

    2013-11-19

    Reduced graphene oxide-azobenzene (RGO-AZO) hybrids were prepared via covalent functionalization for long-term solar thermal storage. Thermal barrier (ΔEa) of cis to tran reversion and thermal storage (ΔH) were improved by molecular hydrogen bonds (H-bonds) through ortho- or para-substitution of AZO. Intramolecular H-bonds thermally stabilized cis-ortho-AZO on RGO with a long-term half-life of 5400 h (ΔEa = 1.2 eV), which was much longer than that of RGO-para-AZO (116 h). RGO-para-AZO with one intermolecular H-bond showed a high density of thermal storage up to 269.8 kJ kg(-1) compared with RGO-ortho-AZO (149.6 kJ kg(-1)) with multiple intra- and intermolecular H-bonds of AZO according to relaxed stable structures. Thermal storage in experiment was the same order magnitude to theoretical data based on ΔH calculated by density functional theory and packing density. Photoactive RGO-AZO hybrid can be developed for high-performance solar thermal storage by optimizing molecular H-bonds.

  13. Dynamic Analysis and Design Optimization of Series Hydraulic Hybrid System through Power Bond Graph Approach

    Directory of Open Access Journals (Sweden)

    R. Ramakrishnan

    2014-01-01

    Full Text Available The availability of natural gas and crude oil resources has been declining over the years. In automobile sector, the consumption of crude oil is 63% of total crude oil production in the world. Hence, automobile industries are placing more emphasis on energy efficient hydraulic hybrid systems, which can replace their conventional transmission systems. Series hydraulic hybrid system (SHHS is a multidomain mechatronics system with two distinct power sources that includes prime mover and hydropneumatic accumulator. It replaces the conventional transmission system to drive the vehicle. The sizing of the subsystems in SHHS plays a major role in improving the energy efficiency of the vehicle. In this paper, a power bond graph approach is used to model the dynamics of the SHHS. The obtained simulation results indicate the energy flow during various modes of operations. It also includes the dynamic response of hydropneumatic accumulator, prime mover, and system output speed. Further, design optimization of the system is carried out to optimize the process parameters for maximizing the system energy efficiency. This leads to increase in fuel economy and environmentally friendly vehicle.

  14. A Functional Approach to User Guides

    DEFF Research Database (Denmark)

    Nielsen, Sandro

    2007-01-01

    draw the user's attention to the different types of use-situations in which the dictionary can help him. When the dictionary functions have been established and the relevant user group has been profiled, the lexicographers will have an excellent basis on which to select the types of information needed...... on lexicography and lexicographic products is the writing of a really crafted and valuable user guide for instance by giving increased consideration to the user perspective. This involves the identification of the functions of the dictionary in terms of communication-oriented and cognitive functions, which helps...... to fulfil the requirements of users. By applying the functional approach lexicographers are forced to reconsider the scope of the user guide. The user guide has traditionally centred on the structures of entries - and consequently on the word list - but its scope should be widened, so as to include all...

  15. Modelling of Non-Linear Pilot Disinfection Water System: A Bond Graph Approach

    Directory of Open Access Journals (Sweden)

    Naoufel ZITOUNI

    2012-08-01

    Full Text Available The ultraviolet (UV irradiations are used to solve the bacteriological problem of the drinking water quality. A discharge-gas lamp is used to produce this type of irradiation. The UV lamp is fed by photovoltaic (PV energy via electronic ballast composed by an inverter, a transformer and resonant circuit (RLC. The aim of this work is to give a useful global model of the system. In particular, we introduce the complicated UV lamp model and the water disinfection kinetics, where the radiant energy flux emitted by the discharge-gas lamp and the arc voltage are a complex functions of the current and time. This system is intended to be mainly used in rural zones, the photovoltaic modules as source of energy is an adequate solution. To optimise the power transfer from the PV array to ballast and UV lamp, a Maximum Power Point Tracking (MPPT device may be located between PV array and the loads. In this paper, we developed a bond-graph model which gives the water quality from UV flow, gas type, pressure, lamp current and geometrical characteristic. Finally reliable simulations are established and compared with experimental tests.

  16. Effect of antibacterial/adhesive approaches on bonding durability of fiber posts cemented with self-etch resin cement.

    Science.gov (United States)

    Shafiei, Fereshteh; Memarpour, Mahtab; Vafamand, Narges; Mohammadi, Mahsa

    2017-09-01

    Longevity of post-retained restoration is highly depended on bonding stability of fiber post (FP) to root dentin. This study evaluated the effect of different antibacterial/adhesive approaches on bonding durability of FPs luted into root canal with a self-etch cement. Seventy-two human maxillary central incisor roots were divided into six groups after endodontic treatment, based on the antibacterial/adhesive treatments as follows: 1)ED primer II (ED, control); 2) Clearfil Protect Bond (PB); 3) 2% chlorhexidine (CH) pretreatment + ED primer II (CH+ED); 4) CH-incorporated into ED primer II (CH in ED); 5) CH pretreatment + Clearfil SE Bond (CH+SE); and 6)CH-incorporated into SE primer (CH in SE). The FPs were then cemented using PanaviaF2.0. After micro-slicing the bonded root dentin, a push-out bond strength (PBS) test was performed immediately or after two years of water storage. Data were analyzed using ANOVA and post hoc Tukey tests (α=0.05). The effects of antibacterial/adhesive approach, time and interaction between the main factors were significant ( p =0.01). There was no significant difference between the immediate groups, except between the CH+ED group (the lowest PBS) and PB and CH in SE groups (the highest PBS) ( p ≤0.03). After aging, the same difference was observed ( p ≤0.02); the control group exhibited a significantly lower PBS compared to the other groups ( p ≤0.01), except for CH+ED. Aging significantly decreased PBS of all the groups ( p ≤0.01); the control group exhibited the highest reduction. CH incorporated into self-etch primers or in pretreatment step prior to two-step self-etch adhesive and antibacterial adhesive could improve bond stability of self-etch cemented fiber post. However, none of these was capable of inhibiting bond degradation over time. Key words: Push-out bond strength, Fiber post, Chlorhexidine.

  17. Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Lewis, Jared; Bergman, Robert; Ellman, Jonathan

    2008-02-04

    Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of

  18. Metal-Ligand Bonds of Second- and Third-Row d-Block Metals Characterized by Density Functional Theory

    Science.gov (United States)

    Jensen, Kasper P.

    2009-08-01

    This paper presents systematic data for 200 neutral diatomic molecules ML (M is a second- or third-row d-block metal and L = H, F, Cl, Br, I, C, N, O, S, or Se) computed with the density functionals TPSSh and BP86. With experimental structures and bond enthalpies available for many of these molecules, the computations first document the high accuracy of TPSSh, giving metal-ligand bond lengths with a mean absolute error of ˜0.01 Å for the second row and 0.03 Å for the third row. TPSSh provides metal-ligand bond enthalpies with mean absolute errors of 37 and 44 kJ/mol for the second- and third-row molecules, respectively. Pathological cases (e.g., HgC and HgN) have errors of up to 155 kJ/mol, more than thrice the mean (observed with both functionals). Importantly, the systematic error component is negligible as measured by a coefficient of the linear regression line of 0.99. Equally important, TPSSh provides uniform accuracy across all three rows of the d-block, which is unprecedented and due to the 10% exact exchange, which is close to optimal for the d-block as a whole. This work provides an accurate and systematic prediction of electronic ground-state spins, characteristic metal-ligand bond lengths, and bond enthalpies for many as yet uncharacterized diatomics, of interest to researchers in the field of second- and third-row d-block chemistry. We stress that the success of TPSSh cannot be naively extrapolated to other special situations such as, e.g., metal-metal bonds. The high accuracy of the procedure further implies that the effective core functions used to model relativistic effects are necessary and sufficient for obtaining accurate geometries and bond enthalpies of second- and third-row molecular systems.

  19. Metal-Ligand Bonds of Second- and Third-Row d-Block Metals Characterized by Density Functional Theory

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2009-01-01

    This paper presents systematic data for 200 neutral diatomic molecules ML (M is it second- or third-row d-block metal and L = H, F, Cl, Br, I, C, N, O, S, or Se) Computed with the density functionals TPSSh and BP86. With experimental Structures and bond enthalpies available for many...... of these molecules, the computations first document the high accuracy of TPSSh, giving metal-ligand bond lengths with a mean absolute error of similar to 0.01 angstrom for the second row and 0.03 angstrom for the third row. TPSSh provides metal-ligand bond enthalpies with mean absolute errors of 37 and 44 k...... metal-ligand bond lengths, and bond enthalpies for many as yet uncharacterized diatomics, of interest to researchers in the field of second- and third-row d-block chemistry. We stress that the success of TPSSh cannot be naively extrapolated to other special situations such as, e.g., metal-metal bonds...

  20. The mechanical bond on carbon nanotubes: diameter-selective functionalization and effects on physical properties.

    Science.gov (United States)

    Martínez-Periñán, Emiliano; de Juan, Alberto; Pouillon, Yann; Schierl, Christoph; Strauss, Volker; Martín, Nazario; Rubio, Ángel; Guldi, Dirk M; Lorenzo, Encarnación; Pérez, Emilio M

    2016-04-28

    We describe the functionalization of SWNTs enriched in (6,5) chirality with electron donating macrocycles to yield rotaxane-type mechanically interlocked carbon nanotubes (MINTs). Investigations by means of electron microscopy and control experiments corroborated the interlocked nature of the MINTs. A comprehensive characterization of the MINTs through UV-vis-NIR, Raman, fluorescence, transient absorption spectroscopy, cyclic voltammetry, and chronoamperometry was carried out. Analyses of the spectroscopic data reveal that the MINT-forming reaction proceeds with diameter selectivity, favoring functionalization of (6,5) SWNTs rather than larger (7,6) SWNTs. In the ground state, we found a lack of significant charge-transfer interactions between the electron donor exTTF and the SWNTs. Upon photoexcitation, efficient charge-transfer between the electron donating exTTF macrocycles and SWNTs was demonstrated. As a complement, we established significantly different charge-transfer rate constants and diffusion coefficients for MINTs and the supramolecular models, which confirms the fundamentally different type of interactions between exTTF and SWNTs in the presence or absence of the mechanical bond. Molecular mechanics and DFT calculations support the experimental findings.

  1. Vibrational signatures of cation-anion hydrogen bonding in ionic liquids: a periodic density functional theory and molecular dynamics study.

    Science.gov (United States)

    Mondal, Anirban; Balasubramanian, Sundaram

    2015-02-05

    Hydrogen bonding in alkylammonium based protic ionic liquids was studied using density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations. Normal-mode analysis within the harmonic approximation and power spectra of velocity autocorrelation functions were used as tools to obtain the vibrational spectra in both the gas phase and the crystalline phases of these protic ionic liquids. The hydrogen bond vibrational modes were identified in the 150-240 cm(-1) region of the far-infrared (far-IR) spectra. A blue shift in the far-IR mode was observed with an increasing number of hydrogen-bonding sites on the cation; the exact peak position is modulated by the cation-anion hydrogen bond strength. Sub-100 cm(-1) bands in the far-IR spectrum are assigned to the rattling motion of the anions. Calculated NMR chemical shifts of the acidic protons in the crystalline phase of these salts also exhibit the signature of cation-anion hydrogen bonding.

  2. Biomimetic multidirectional scaffolds for zonal osteochondral tissue engineering via a lyophilization bonding approach.

    Science.gov (United States)

    Clearfield, Drew; Nguyen, Andrew; Wei, Mei

    2018-04-01

    The zonal organization of osteochondral tissue underlies its long term function. Despite this, tissue engineering strategies targeted for osteochondral repair commonly rely on the use of isotropic biomaterials for tissue reconstruction. There exists a need for a new class of highly biomimetic, anisotropic scaffolds that may allow for the engineering of new tissue with zonal properties. To address this need, we report the facile production of monolithic multidirectional collagen-based scaffolds that recapitulate the zonal structure and composition of osteochondral tissue. First, superficial and osseous zone-mimicking scaffolds were fabricated by unidirectional freeze casting collagen-hyaluronic acid and collagen-hydroxyapatite-containing suspensions, respectively. Following their production, a lyophilization bonding process was used to conjoin these scaffolds with a distinct collagen-hyaluronic acid suspension mimicking the composition of the transition zone. Resulting matrices contained a thin, highly aligned superficial zone that interfaced with a cellular transition zone and vertically oriented calcified cartilage and osseous zones. Confocal microscopy confirmed a zone-specific localization of hyaluronic acid, reflecting the depth-dependent increase of glycosaminoglycans in the native tissue. Poorly crystalline, carbonated hydroxyapatite was localized to the calcified cartilage and osseous zones and bordered the transition zone. Compressive testing of hydrated scaffold zones confirmed an increase of stiffness with scaffold depth, where compressive moduli of chondral and osseous zones fell within or near ranges conducive for chondrogenesis or osteogenesis of mesenchymal stem cells. With the combination of these biomimetic architectural and compositional cues, these multidirectional scaffolds hold great promise for the engineering of zonal osteochondral tissue. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 948-958, 2018. © 2017 Wiley Periodicals

  3. Moisture effect on interfacial integrity of epoxy-bonded system: a hierarchical approach

    Science.gov (United States)

    Tam, Lik-ho; Lun Chow, Cheuk; Lau, Denvid

    2018-01-01

    The epoxy-bonded system has been widely used in various applications across different scale lengths. Prior investigations have indicated that the moisture-affected interfacial debonding is the major failure mode of such a system, but the fundamental mechanism remains unknown, such as the basis for the invasion of water molecules in the cross-linked epoxy and the epoxy-bonded interface. This prevents us from predicting the long-term performance of the epoxy-related applications under the effect of the moisture. Here, we use full atomistic models to investigate the response of the epoxy-bonded system towards the adhesion test, and provide a detailed analysis of the interfacial integrity under the moisture effect and the associated debonding mechanism. Molecular dynamics simulations show that water molecules affect the hierarchical structure of the epoxy-bonded system at the nanoscale by disrupting the film-substrate interaction and the molecular interaction within the epoxy, which leads to the detachment of the epoxy thin film, and the final interfacial debonding. The simulation results show good agreement with the experimental results of the epoxy-bonded system. Through identifying the relationship between the epoxy structure and the debonding mechanism at multiple scales, it is shown that the hierarchical structure of the epoxy-bonded system is crucial for the interfacial integrity. In particular, the available space of the epoxy-bonded system, which consists of various sizes ranging from the atomistic scale to the macroscale and is close to the interface facilitates the moisture accumulation, leading to a distinct interfacial debonding when compared to the dry scenario.

  4. Craniofacial fibrous dysplasia surgery: a functional approach.

    Science.gov (United States)

    Béquignon, E; Cardinne, C; Lachiver, X; Wagner, I; Chabolle, F; Baujat, B

    2013-09-01

    Craniofacial fibrous dysplasia has not only esthetic but functional impact. Surgery is controversial, ranging from conservative to radical. It involves elevated hemorrhage risk, and should be progressive, based on an individual risk/benefit analysis with the aim of improving quality of life. Three patients (one male, two female; mean age, 35 years) with evolutive orbital-temporal maxillary dysplasia were treated between 2008 and 2009 in our department. All showed exophthalmia and nasal obstruction. In one patient, symptomatology was aggravated by a frontal sinus cyst within the dysplasia. Another had associated auditory canal obstruction inducing recurrent external otitis. Optic nerve decompression was achieved on a combined coronal and endonasal approach, assisted by neuronavigation. Complementary remodelling resection, dacryocystorhinostomy and internal optic nerve decompression were performed. Functional results showed 70 % improvement on a subjective scale for eye tension and nasal obstruction. Surgery was feasible in all patients, with no complications. Current surgical management allies esthetic and functional concerns. Remodeling resection is the reference technique. The coronal approach is a good primary option for optic nerve decompression. Endonasal surgery with neuronavigation improves nasal ventilation and lacrimal canal permeability. Copyright © 2012 Elsevier Masson SAS. All rights reserved.

  5. A Pseudo MS3 Approach for Identification of Disulfide-Bonded Proteins: Uncommon Product Ions and Database Search

    Science.gov (United States)

    Chen, Jianzhong; Shiyanov, Pavel; Schlager, John J.; Green, Kari B.

    2012-02-01

    It has previously been reported that disulfide and backbone bonds of native intact proteins can be concurrently cleaved using electrospray ionization (ESI) and collision-induced dissociation (CID) tandem mass spectrometry (MS/MS). However, the cleavages of disulfide bonds result in different cysteine modifications in product ions, making it difficult to identify the disulfide-bonded proteins via database search. To solve this identification problem, we have developed a pseudo MS3 approach by combining nozzle-skimmer dissociation (NSD) and CID on a quadrupole time-of-flight (Q-TOF) mass spectrometer using chicken lysozyme as a model. Although many of the product ions were similar to those typically seen in MS/MS spectra of enzymatically derived peptides, additional uncommon product ions were detected including ci-1 ions (the ith residue being aspartic acid, arginine, lysine and dehydroalanine) as well as those from a scrambled sequence. The formation of these uncommon types of product ions, likely caused by the lack of mobile protons, were proposed to involve bond rearrangements via a six-membered ring transition state and/or salt bridge(s). A search of 20 pseudo MS3 spectra against the Gallus gallus (chicken) database using Batch-Tag, a program originally designed for bottom up MS/MS analysis, identified chicken lysozyme as the only hit with the expectation values less than 0.02 for 12 of the spectra. The pseudo MS3 approach may help to identify disulfide-bonded proteins and determine the associated post-translational modifications (PTMs); the confidence in the identification may be improved by incorporating the fragmentation characteristics into currently available search programs.

  6. Density functional for van der Waals forces accounts for hydrogen bond in benchmark set of water hexamers

    DEFF Research Database (Denmark)

    Kelkkanen, Kari André; Lundqvist, Bengt; Nørskov, Jens Kehlet

    2009-01-01

    A recent extensive study has investigated how various exchange-correlation (XC) functionals treat hydrogen bonds in water hexamers and has shown traditional generalized gradient approximation and hybrid functionals used in density-functional (DF) theory to give the wrong dissociation-energy trend...... of low-lying isomers and van der Waals (vdW) dispersion forces to give key contributions to the dissociation energy. The question raised whether functionals that incorporate vdW forces implicitly into the XC functional predict the correct lowest-energy structure for the water hexamer and yield accurate...

  7. A new simplifying approach to molecular geometry description: the vectorial bond-valence model.

    Science.gov (United States)

    Harvey, Miguel Angel; Baggio, Sergio; Baggio, Ricardo

    2006-12-01

    A method to describe, analyze and even predict the coordination geometries of metal complexes is proposed, based on previous well established concepts such as bond valence and valence-shell electron-pair repulsion (VSEPR). The idea behind the method is the generalization of the scalar bond-valence concept into a vector quantity, the bond-valence vector (BVV), with the innovation that the multidentate ligands are represented by their resultant BVVs. Complex n-ligand coordination spheres (frequently indescribable at the atomic level) reduce to much simpler ones when analyzed in BVV space, with the bonus of a better applicability of the VSEPR predictions. The geometrical implications of the BVV description are analyzed for the cases of n=2 and 3 (n=number of ligands), and the validity of its predictions, checked for a large number of metal complexes.

  8. International Space Station Centrifuge Rotor Models A Comparison of the Euler-Lagrange and the Bond Graph Modeling Approach

    Science.gov (United States)

    Nguyen, Louis H.; Ramakrishnan, Jayant; Granda, Jose J.

    2006-01-01

    The assembly and operation of the International Space Station (ISS) require extensive testing and engineering analysis to verify that the Space Station system of systems would work together without any adverse interactions. Since the dynamic behavior of an entire Space Station cannot be tested on earth, math models of the Space Station structures and mechanical systems have to be built and integrated in computer simulations and analysis tools to analyze and predict what will happen in space. The ISS Centrifuge Rotor (CR) is one of many mechanical systems that need to be modeled and analyzed to verify the ISS integrated system performance on-orbit. This study investigates using Bond Graph modeling techniques as quick and simplified ways to generate models of the ISS Centrifuge Rotor. This paper outlines the steps used to generate simple and more complex models of the CR using Bond Graph Computer Aided Modeling Program with Graphical Input (CAMP-G). Comparisons of the Bond Graph CR models with those derived from Euler-Lagrange equations in MATLAB and those developed using multibody dynamic simulation at the National Aeronautics and Space Administration (NASA) Johnson Space Center (JSC) are presented to demonstrate the usefulness of the Bond Graph modeling approach for aeronautics and space applications.

  9. Exploration of C–H and N–H-bond functionalization towards 1-(1,2-diarylindol-3-yltetrahydroisoquinolines

    Directory of Open Access Journals (Sweden)

    Michael Ghobrial

    2014-09-01

    Full Text Available The synthesis of 1,2,3-trisubstituted indoles was investigated. More specifically, straightforward synthetic routes towards 1-(1,2-diarylindol-3-yl-N-PG-THIQs (PG = protecting group, THIQ = tetrahydroisoquinoline employing transition metal-catalyzed C–H and N–H-bond functionalization were explored. It was found that the synthesis of the target compounds is strongly dependent on the order of events. Hence, depending on the requirements of a synthetic problem the most suitable and promising pathway can be chosen. Additionally, a new synthetic approach towards 1,2-diarylindoles starting from 1-arylindole could be established in the course of our investigation by using a palladium-catalyzed protocol. Such 1,2-diarylindoles were successfully reacted with N-Boc-THIQ to furnish 1,2,3-trisubstituted indoles as target compounds. Furthermore, regioselective N-arylation of protected and unprotected 1-(indol-3-yl-THIQs was successfully conducted using either simple iron or copper salts as catalysts.

  10. Substituent Effects on the Stability of Thallium and Phosphorus Triple Bonds: A Density Functional Study.

    Science.gov (United States)

    Lu, Jia-Syun; Yang, Ming-Chung; Su, Ming-Der

    2017-07-05

    Three computational methods (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ+dp) were used to study the effect of substitution on the potential energy surfaces of RTl≡PR (R = F, OH, H, CH₃, SiH₃, SiMe(Si t Bu₃)₂, Si i PrDis₂, Tbt (=C₆H₂-2,4,6-(CH(SiMe₃)₂)₃), and Ar* (=C₆H₃-2,6-(C₆H₂-2, 4,6- i -Pr₃)₂)). The theoretical results show that these triply bonded RTl≡PR compounds have a preference for a bent geometry (i.e., ∠R⎼Tl⎼P ≈ 180° and ∠Tl⎼P⎼R ≈ 120°). Two valence bond models are used to interpret the bonding character of the Tl≡P triple bond. One is model [I], which is best described as TlP. This interprets the bonding conditions for RTl≡PR molecules that feature small ligands. The other is model [II], which is best represented as TlP. This explains the bonding character of RTl≡PR molecules that feature large substituents. Irrespective of the types of substituents used for the RTl≡PR species, the theoretical investigations (based on the natural bond orbital, the natural resonance theory, and the charge decomposition analysis) demonstrate that their Tl≡P triple bonds are very weak. However, the theoretical results predict that only bulkier substituents greatly stabilize the triply bonded RTl≡PR species, from the kinetic viewpoint.

  11. Development of simulation approach for two-dimensional chiral molecular self-assembly driven by hydrogen bond at the liquid/solid interface

    Science.gov (United States)

    Qin, Yuan; Yao, Man; Hao, Ce; Wan, Lijun; Wang, Yunhe; Chen, Ting; Wang, Dong; Wang, Xudong; Chen, Yonggang

    2017-09-01

    Two-dimensional (2D) chiral self-assembly system of 5-(benzyloxy)-isophthalic acid derivative/(S)-(+)-2-octanol/highly oriented pyrolytic graphite was studied. A combined density functional theory/molecular mechanics/molecular dynamics (DFT/MM/MD) approach for system of 2D chiral molecular self-assembly driven by hydrogen bond at the liquid/solid interface was thus proposed. Structural models of the chiral assembly were built on the basis of scanning tunneling microscopy (STM) images and simplified for DFT geometry optimization. Merck Molecular Force Field (MMFF) was singled out as the suitable force field by comparing the optimized configurations of MM and DFT. MM and MD simulations for hexagonal unit model which better represented the 2D assemble network were then preformed with MMFF. The adhesion energy, evolution of self-assembly process and characteristic parameters of hydrogen bond were obtained and analyzed. According to the above simulation, the stabilities of the clockwise and counterclockwise enantiomorphous networks were evaluated. The calculational results were supported by STM observations and the feasibility of the simulation method was confirmed by two other systems in the presence of chiral co-absorbers (R)-(-)-2-octanol and achiral co-absorbers 1-octanol. This theoretical simulation method assesses the stability trend of 2D enantiomorphous assemblies with atomic scale and can be applied to the similar hydrogen bond driven 2D chirality of molecular self-assembly system.

  12. Effect of a functional monomer (MDP) on the enamel bond durability of single-step self-etch adhesives.

    Science.gov (United States)

    Tsuchiya, Kenji; Takamizawa, Toshiki; Barkmeier, Wayne W; Tsubota, Keishi; Tsujimoto, Akimasa; Berry, Thomas P; Erickson, Robert L; Latta, Mark A; Miyazaki, Masashi

    2016-02-01

    The present study aimed to determine the effect of the functional monomer, 10-methacryloxydecyl dihydrogen phosphate (MDP), on the enamel bond durability of single-step self-etch adhesives through integrating fatigue testing and long-term water storage. An MDP-containing self-etch adhesive, Clearfil Bond SE ONE (SE), and an experimental adhesive, MDP-free (MF), which comprised the same ingredients as SE apart from MDP, were used. Shear bond strength (SBS) and shear fatigue strength (SFS) were measured with or without phosphoric acid pre-etching. The specimens were stored in distilled water for 24 h, 6 months, or 1 yr. Although similar SBS and SFS values were obtained for SE with pre-etching and for MF after 24 h of storage in distilled water, SE with pre-etching showed higher SBS and SFS values than MF after storage in water for 6 months or 1 yr. Regardless of the pre-etching procedure, SE showed higher SBS and SFS values after 6 months of storage in distilled water than after 24 h or 1 yr. To conclude, MDP might play an important role in enhancing not only bond strength but also bond durability with respect to repeated subcritical loading after long-term water storage. © 2015 Eur J Oral Sci.

  13. A theoretical perspective of the nature of hydrogen-bond types - the atoms in molecules approach

    Czech Academy of Sciences Publication Activity Database

    Pandiyan, B. V.; Kolandaivel, P.; Deepa, Palanisamy

    2014-01-01

    Roč. 112, č. 12 (2014), s. 1609-1623 ISSN 0026-8976 Institutional support: RVO:61388963 Keywords : hydrogen bond * proton affinity * deprotanation enthalpy * atoms in molecules * chemical shift Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.720, year: 2014

  14. Pd-Catalyzed C-H Bond Functionalization on the Indole and Pyrrole Nucleus

    Science.gov (United States)

    Beck, Elizabeth M.; Gaunt, Matthew J.

    This review details recent developments in the Pd-catalyzed C-H bond arylation and alkenylation of indoles and pyrroles, aromatic heterocycles that are frequently displayed in natural products and medicinal agents.

  15. Detection of discriminative sequence patterns in the neighborhood of proline cis peptide bonds and their functional annotation

    Directory of Open Access Journals (Sweden)

    Papaloukas Costas

    2009-04-01

    Full Text Available Abstract Background Polypeptides are composed of amino acids covalently bonded via a peptide bond. The majority of peptide bonds in proteins is found to occur in the trans conformation. In spite of their infrequent occurrence, cis peptide bonds play a key role in the protein structure and function, as well as in many significant biological processes. Results We perform a systematic analysis of regions in protein sequences that contain a proline cis peptide bond in order to discover non-random associations between the primary sequence and the nature of proline cis/trans isomerization. For this purpose an efficient pattern discovery algorithm is employed which discovers regular expression-type patterns that are overrepresented (i.e. appear frequently repeated in a set of sequences. Four types of pattern discovery are performed: i exact pattern discovery, ii pattern discovery using a chemical equivalency set, iii pattern discovery using a structural equivalency set and iv pattern discovery using certain amino acids' physicochemical properties. The extracted patterns are carefully validated using a specially implemented scoring function and a significance measure (i.e. log-probability estimate indicative of their specificity. The score threshold for the first three types of pattern discovery is 0.90 while for the last type of pattern discovery 0.80. Regarding the significance measure, all patterns yielded values in the range [-9, -31] which ensure that the derived patterns are highly unlikely to have emerged by chance. Among the highest scoring patterns, most of them are consistent with previous investigations concerning the neighborhood of cis proline peptide bonds, and many new ones are identified. Finally, the extracted patterns are systematically compared against the PROSITE database, in order to gain insight into the functional implications of cis prolyl bonds. Conclusion Cis patterns with matches in the PROSITE database fell mostly into two

  16. Nickel Superoxide Dismutase: Structural and Functional Roles of His1 and its H-bonding Network

    Science.gov (United States)

    Ryan, Kelly C.; Guce, Abigail I.; Johnson, Olivia E.; Brunold, Thomas C.; Cabelli, Diane E.; Garman, Scott C.; Maroney, Michael J.

    2015-01-01

    Crystal structures of nickel-dependent superoxide dismutases (NiSODs) reveal the presence of a H-bonding network formed between the N-H of the apical imidazole ligand from His1 and the Glu17 carboxylate from a neighboring subunit in the hexameric enzyme. This interaction is supported by another intra-subunit H-bond between Glu17 and Arg47. In this study, four mutant NiSOD proteins were produced to experimentally evaluate the roles of this H-bonding network, and compare the results with prior predictions from DFT calculations. H1A-NiSOD, which lacks the apical ligand entirely, was crystallographically characterized and reveals that in the absence of the Glu17-His1 H-bond, the active site is disordered. Subsequent characterization using X-ray absorption spectroscopy (XAS) shows that Ni(II) is bound in the expected N2S2 planar coordination site. Despite these structural perturbations, the H1A-NiSOD variant is an active catalyst with 4% of WT-NiSOD activity. Three other mutations were designed to preserve the apical imidazole ligand, but perturb the H-bonding network: R47A-NiSOD, lacks the intra-molecular H-bonding interaction, E17R/R47A-NiSOD, which retains the intra-molecular H-bond, but lacks the inter-molecular Glu17-His1 H-bond, and E17A/R47A-NiSOD, which lacks both H-bonding interactions. These variants were characterized by a combination of techniques including XAS characterization of the nickel site structure, kinetic studies employing pulse-radiolytic production of superoxide, and EPR and chemical probes of the redox activity. The results indicate that in addition to the roles in redox tuning suggested by the computational models, the Glu17-His1 H-bond plays an important structural role in the formation of the Ni-hook motif that is a critical feature of the active site. PMID:25580509

  17. Approach to ''Mind'' using functional neuroimaging

    International Nuclear Information System (INIS)

    Matsuda, Hiroshi

    2006-01-01

    This review mainly describes authors' recent investigations concerning neuroimages approaching to even human ''mind'' using techniques of PET, SPECT and functional MRI (fMRI). Progress of such studies greatly owes to the development of image statistics of the brain like statistical parametric mapping (www.fil.ion.ucl.ac.uk/spm/), and brain standards (www.mrc-cbu.cam.ac.uk/Imaging/mnispace.html, and ric.uthscsa.edu/projects/talairach daemon.html). The author discusses and presents images in cases of hallucinations (SPECT and H 2 15 O-PET), autism (SPECT), sleep, depression, and its therapy by transcaranial magnetic stimulation. These studies are expected to contribute to diagnosis and therapy of endogenous neurological disorders. (T.I.)

  18. Quantum anharmonic oscillator: The airy function approach

    Energy Technology Data Exchange (ETDEWEB)

    Maiz, F., E-mail: fethimaiz@gmail.com [King Khalid University, Faculty of Science, Physics Department, PO Box 9004, Abha 61413, Asseer (Saudi Arabia); University of Cartage, Nabeul Engineering Preparatory Institute, Merazka, 8000 Nabeul (Tunisia); AlFaify, S. [King Khalid University, Faculty of Science, Physics Department, PO Box 9004, Abha 61413, Asseer (Saudi Arabia)

    2014-05-15

    New and simple numerical method is being reported to solve anharmonic oscillator problems. The method is setup to approach the real potential V(x) of the anharmonic oscillator system as a piecewise linear potential u(x) and to solve the Schrödinger equation of the system using the Airy function. Then, solutions continuity conditions lead to the energy quantification condition, and consequently, the energy eigenvalues. For testing purpose, the method was applied on the sextic and octic oscillators systems. The proposed method is found to be realistic, computationally simple, and having high degrees of accuracy. In addition, it can be applied to any form of potential. The results obtained by the proposed method were seen closely agreeing with results reached by other complicated methods.

  19. On The Nature of the Halogen Bond.

    Science.gov (United States)

    Wang, Changwei; Danovich, David; Mo, Yirong; Shaik, Sason

    2014-09-09

    The wide-ranging applications of the halogen bond (X-bond), notably in self-assembling materials and medicinal chemistry, have placed this weak intermolecular interaction in a center of great deal of attention. There is a need to elucidate the physical nature of the halogen bond for better understanding of its similarity and differences vis-à-vis other weak intermolecular interactions, for example, hydrogen bond, as well as for developing improved force-fields to simulate nano- and biomaterials involving X-bonds. This understanding is the focus of the present study that combines the insights of a bottom-up approach based on ab initio valence bond (VB) theory and the block-localized wave function (BLW) theory that uses monomers to reconstruct the wave function of a complex. To this end and with an aim of unification, we studied the nature of X-bonds in 55 complexes using the combination of VB and BLW theories. Our conclusion is clear-cut; most of the X-bonds are held by charge transfer interactions (i.e., intermolecular hyperconjugation) as envisioned more than 60 years ago by Mulliken. This is consistent with the experimental and computational findings that X-bonds are more directional than H-bonds. Furthermore, the good linear correlation between charge transfer energies and total interaction energies partially accounts for the success of simple force fields in the simulation of large systems involving X-bonds.

  20. A time-dependent density functional theory study on the effect of electronic excited-state hydrogen bonding on luminescent MOFs.

    Science.gov (United States)

    Ji, Min; Hao, Ce; Wang, Dandan; Li, Hongjiang; Qiu, Jieshan

    2013-03-14

    We have investigated a new silver-based luminescent metal-organic framework (MOF) using density functional theory and time-dependent density functional theory methods. We theoretically demonstrated that the H...O hydrogen bond is strengthened and the Ag-O coordination bond is shortened significantly due to strengthening of the hydrogen bond in the S(1) state. When the hydrogen bond is formed, the mechanism of luminescence changes from a ligand-to-metal charge transfer (LMCT) coupled with intraligand charge transfer (LLCT) to LMCT, and the luminescence is found to be enhanced.

  1. ``Green's function'' approach & low-mode asymmetries

    Science.gov (United States)

    Masse, Laurent; Clark, Dan; Salmonson, Jay; MacLaren, Steve; Ma, Tammy; Khan, Shahab; Pino, Jesse; Ralph, Jo; Czajka, C.; Tipton, Robert; Landen, Otto; Kyrala, Georges; 2 Team; 1 Team

    2017-10-01

    Long wavelength, low mode asymmetries are believed to play a leading role in limiting the performance of current ICF implosions on NIF. These long wavelength modes are initiated and driven by asymmetries in the x-ray flux from the hohlraum; however, the underlying hydrodynamics of the implosion also act to amplify these asymmetries. The work presented here aim to deepen our understanding of the interplay of the drive asymmetries and the underlying implosion hydrodynamics in determining the final imploded configuration. This is accomplished through a synthesis of numerical modeling, analytic theory, and experimental data. In detail, we use a Green's function approach to connect the drive asymmetry seen by the capsule to the measured inflight and hot spot symmetries. The approach has been validated against a suite of numerical simulations. Ultimately, we hope this work will identify additional measurements to further constrain the asymmetries and increase hohlraum illumination design flexibility on the NIF. The technique and derivation of associated error bars will be presented. LLC, (LLNS) Contract No. DE-AC52-07NA27344.

  2. A metallization and bonding approach for high performance carbon nanotube thermal interface materials

    International Nuclear Information System (INIS)

    Cross, Robert; Graham, Samuel; Cola, Baratunde A; Fisher, Timothy; Xu Xianfan; Gall, Ken

    2010-01-01

    A method has been developed to create vertically aligned carbon nanotube (VACNT) thermal interface materials that can be attached to a variety of metallized surfaces. VACNT films were grown on Si substrates using standard CVD processing followed by metallization using Ti/Au. The coated CNTs were then bonded to metallized substrates at 220 deg. C. By reducing the adhesion of the VACNTs to the growth substrate during synthesis, the CNTs can be completely transferred from the Si growth substrate and used as a die attachment material for electronic components. Thermal resistance measurements using a photoacoustic technique showed thermal resistances as low as 1.7 mm 2 K W -1 for bonded VACNT films 25-30 μm in length and 10 mm 2 K W -1 for CNTs up to 130 μm in length. Tensile testing demonstrated a die attachment strength of 40 N cm -2 at room temperature. Overall, these metallized and bonded VACNT films demonstrate properties which are promising for next-generation thermal interface material applications.

  3. Proton dynamics in the strong chelate hydrogen bond of crystalline picolinic acid N-oxide. A new computational approach and infrared, raman and INS study.

    Science.gov (United States)

    Stare, Jernej; Panek, Jarosław; Eckert, Juergen; Grdadolnik, Joze; Mavri, Janez; Hadzi, Dusan

    2008-02-21

    Infrared, Raman and INS spectra of picolinic acid N-oxide (PANO) were recorded and examined for the location of the hydronic modes, particularly O-H stretching and COH bending. PANO is representative of strong chelate hydrogen bonds (H-bonds) with its short O...O distance (2.425 A). H-bonding is possibly well-characterized by diffraction, NMR and NQR data and calculated potential energy functions. The analysis of the spectra is assisted by DFT frequency calculations both in the gas phase and in the solid state. The Car-Parrinello quantum mechanical solid-state method is also used for the proton dynamics simulation; it shows the hydron to be located about 99% of time in the energy minimum near the carboxylic oxygen; jumps to the N-O acceptor are rare. The infrared spectrum excels by an extended absorption (Zundel's continuum) interrupted by numerous Evans transmissions. The model proton potential functions on which the theories of continuum formation are based do not correspond to the experimental and computed characteristics of the hydrogen bond in PANO, therefore a novel approach has been developed; it is based on crystal dynamics driven hydronium potential fluctuation. The envelope of one hundred 0 --> 1 OH stretching transitions generated by molecular dynamics simulation exhibits a maximum at 1400 cm-1 and a minor hump at approximately 1600 cm-1. These positions square well with ones predicted for the COH bending and OH stretching frequencies derived from various one- and two-dimensional model potentials. The coincidences with experimental features have to be considered with caution because the CPMD transition envelope is based solely on the OH stretching coordinate while the observed infrared bands correspond to heavily mixed modes as was previously shown by the normal coordinate analysis of the IR spectrum of argon matrix isolated PANO, the present CPMD frequency calculation and the empirical analysis of spectra. The experimental infrared spectra show some

  4. Effect on push-out bond strength of glass-fiber posts functionalized with polydopamine using different adhesives.

    Science.gov (United States)

    Chen, Qian; Cai, Qing; Li, Yan; Wei, Xu-Yi; Huang, Zhi; Wang, Xin-Zhi

    2014-04-01

    To evaluate the push-out bond strengths of prefabricated glass-fiber posts (Beijing Oya Biomaterials) with polydopamine functionalized to root dentin using two different resin cements (Paracore and RelyX Unicem) in different root regions (cervical, middle, and apical). Forty extracted human, single-rooted teeth were endodontically treated and a 9-mm post space was prepared in each tooth with post drills provided by the manufacturer. Specimens were then randomly assigned into four groups (n = 10 per group), depending on the adhesive system and post surface treatment used: group IA (Paracore + polydopamine); group IB (Paracore + control); group IIA (RelyX Unicem + polydopamine); group IIB (RelyX Unicem + control). Following post cementation, the specimens were stored in distilled water at 37°C for 7 days. The push-out test was performed using a universal testing machine (0.5 mm/ min), and the failure modes were examined with a stereomicroscope. Data were statistically analyzed using twoway ANOVA (p = 0.05). Bond strengths (mean ± SD) were: 7.909 ± 3.166 MPa (group IA), 4.675 ± 2.170 MPa (group IB), 8.186 ± 2.766 MPa (group IIA), 4.723 ± 2.084 MPa (group IIB). The bond strength of polydopamine groups was significantly higher than one of the control groups (p 0.05). Stereomicroscopic analysis showed a higher percentage of adhesive than cohesive failures in all groups. Surface polydopamine functionalization was confirmed to be a reliable method for improving the bond strength of resin luting agents to fiber posts. The bond strength of Paracore to fiber posts was not significantly different from that of RelyX Unicem, and considering its convenient application, Paracore can be recommended.

  5. A comprehensive analysis of molecule-intrinsic quasi-atomic, bonding, and correlating orbitals. I. Hartree-Fock wave functions

    International Nuclear Information System (INIS)

    West, Aaron C.; Schmidt, Michael W.; Gordon, Mark S.; Ruedenberg, Klaus

    2013-01-01

    Through a basis-set-independent web of localizing orbital-transformations, the electronic wave function of a molecule is expressed in terms of a set of orbitals that reveal the atomic structure and the bonding pattern of a molecule. The analysis is based on resolving the valence orbital space in terms of an internal space, which has minimal basis set dimensions, and an external space. In the internal space, oriented quasi-atomic orbitals and split-localized molecular orbitals are determined by new, fast localization methods. The density matrix between the oriented quasi-atomic orbitals as well as the locations of the split-localized orbitals exhibit atomic populations and inter-atomic bonding patterns. A correlation-adapted quasi-atomic basis is determined in the external orbital space. The general formulations are specified in detail for Hartree-Fock wave functions. Applications to specific molecules exemplify the general scheme

  6. Halogen bonding from a hard and soft acids and bases perspective: investigation by using density functional theory reactivity indices.

    Science.gov (United States)

    Pinter, Balazs; Nagels, Nick; Herrebout, Wouter A; De Proft, Frank

    2013-01-07

    Halogen bonds between the trifluoromethyl halides CF(3)Cl, CF(3)Br and CF(3)I, and dimethyl ether, dimethyl sulfide, trimethylamine and trimethyl phosphine were investigated using Pearson's hard and soft acids and bases (HSAB) concept with conceptual DFT reactivity indices, the Ziegler-Rauk-type energy-decomposition analysis, the natural orbital for chemical valence (NOCV) framework and the non-covalent interaction (NCI) index. It is found that the relative importance of electrostatic and orbital (charge transfer) interactions varies as a function of both the donor and acceptor molecules. Hard and soft interactions were distinguished and characterised by atomic charges, electrophilicity and local softness indices. Dual-descriptor plots indicate an orbital σ hole on the halogen similar to the electrostatic σ hole manifested in the molecular electrostatic potential. The predicted high halogen-bond-acceptor affinity of N-heterocyclic carbenes was evidenced in the highest complexation energy for the hitherto unknown CF(3) I·NHC complex. The dominant NOCV orbital represents an electron-density deformation according to a n→σ*-type interaction. The characteristic signal found in the reduced density gradient versus electron-density diagram corresponds to the non-covalent interaction between contact atoms in the NCI plots, which is the manifestation of halogen bonding within the NCI theory. The unexpected C-X bond strengthening observed in several cases was rationalised within the molecular orbital framework. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. A computational approach for the annotation of hydrogen-bonded base interactions in crystallographic structures of the ribozymes

    Science.gov (United States)

    Hamdani, Hazrina Yusof; Artymiuk, Peter J.; Firdaus-Raih, Mohd

    2015-09-01

    A fundamental understanding of the atomic level interactions in ribonucleic acid (RNA) and how they contribute towards RNA architecture is an important knowledge platform to develop through the discovery of motifs from simple arrangements base pairs, to more complex arrangements such as triples and larger patterns involving non-standard interactions. The network of hydrogen bond interactions is important in connecting bases to form potential tertiary motifs. Therefore, there is an urgent need for the development of automated methods for annotating RNA 3D structures based on hydrogen bond interactions. COnnection tables Graphs for Nucleic ACids (COGNAC) is automated annotation system using graph theoretical approaches that has been developed for the identification of RNA 3D motifs. This program searches for patterns in the unbroken networks of hydrogen bonds for RNA structures and capable of annotating base pairs and higher-order base interactions, which ranges from triples to sextuples. COGNAC was able to discover 22 out of 32 quadruples occurrences of the Haloarcula marismortui large ribosomal subunit (PDB ID: 1FFK) and two out of three occurrences of quintuple interaction reported by the non-canonical interactions in RNA (NCIR) database. These and several other interactions of interest will be discussed in this paper. These examples demonstrate that the COGNAC program can serve as an automated annotation system that can be used to annotate conserved base-base interactions and could be added as additional information to established RNA secondary structure prediction methods.

  8. A computational approach for the annotation of hydrogen-bonded base interactions in crystallographic structures of the ribozymes

    International Nuclear Information System (INIS)

    Hamdani, Hazrina Yusof; Artymiuk, Peter J.; Firdaus-Raih, Mohd

    2015-01-01

    A fundamental understanding of the atomic level interactions in ribonucleic acid (RNA) and how they contribute towards RNA architecture is an important knowledge platform to develop through the discovery of motifs from simple arrangements base pairs, to more complex arrangements such as triples and larger patterns involving non-standard interactions. The network of hydrogen bond interactions is important in connecting bases to form potential tertiary motifs. Therefore, there is an urgent need for the development of automated methods for annotating RNA 3D structures based on hydrogen bond interactions. COnnection tables Graphs for Nucleic ACids (COGNAC) is automated annotation system using graph theoretical approaches that has been developed for the identification of RNA 3D motifs. This program searches for patterns in the unbroken networks of hydrogen bonds for RNA structures and capable of annotating base pairs and higher-order base interactions, which ranges from triples to sextuples. COGNAC was able to discover 22 out of 32 quadruples occurrences of the Haloarcula marismortui large ribosomal subunit (PDB ID: 1FFK) and two out of three occurrences of quintuple interaction reported by the non-canonical interactions in RNA (NCIR) database. These and several other interactions of interest will be discussed in this paper. These examples demonstrate that the COGNAC program can serve as an automated annotation system that can be used to annotate conserved base-base interactions and could be added as additional information to established RNA secondary structure prediction methods

  9. A computational approach for the annotation of hydrogen-bonded base interactions in crystallographic structures of the ribozymes

    Energy Technology Data Exchange (ETDEWEB)

    Hamdani, Hazrina Yusof, E-mail: hazrina@mfrlab.org [School of Biosciences and Biotechnology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi (Malaysia); Advanced Medical and Dental Institute, Universiti Sains Malaysia, Bertam, Kepala Batas (Malaysia); Artymiuk, Peter J., E-mail: p.artymiuk@sheffield.ac.uk [Dept. of Molecular Biology and Biotechnology, Firth Court, University of Sheffield, S10 T2N Sheffield (United Kingdom); Firdaus-Raih, Mohd, E-mail: firdaus@mfrlab.org [School of Biosciences and Biotechnology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi (Malaysia)

    2015-09-25

    A fundamental understanding of the atomic level interactions in ribonucleic acid (RNA) and how they contribute towards RNA architecture is an important knowledge platform to develop through the discovery of motifs from simple arrangements base pairs, to more complex arrangements such as triples and larger patterns involving non-standard interactions. The network of hydrogen bond interactions is important in connecting bases to form potential tertiary motifs. Therefore, there is an urgent need for the development of automated methods for annotating RNA 3D structures based on hydrogen bond interactions. COnnection tables Graphs for Nucleic ACids (COGNAC) is automated annotation system using graph theoretical approaches that has been developed for the identification of RNA 3D motifs. This program searches for patterns in the unbroken networks of hydrogen bonds for RNA structures and capable of annotating base pairs and higher-order base interactions, which ranges from triples to sextuples. COGNAC was able to discover 22 out of 32 quadruples occurrences of the Haloarcula marismortui large ribosomal subunit (PDB ID: 1FFK) and two out of three occurrences of quintuple interaction reported by the non-canonical interactions in RNA (NCIR) database. These and several other interactions of interest will be discussed in this paper. These examples demonstrate that the COGNAC program can serve as an automated annotation system that can be used to annotate conserved base-base interactions and could be added as additional information to established RNA secondary structure prediction methods.

  10. Characterization of the Bonds Developed between Calcium Silicate Hydrate and Polycarboxylate-Based Superplasticizers with Silyl Functionalities

    KAUST Repository

    Orozco, Carlos A.

    2017-03-24

    Major developments in concrete technology have been achieved with the use of polycarboxylate-based superplasticizers (PCEs) to improve the concrete rheology without increasing the mix water content. Currently, it is possible to control the fluidity of the fresh concrete and obtain stronger and more durable structures. Therefore, there is a strong incentive to understand the interactions between PCEs and cement hydrates at the atomic scale to design new customized functional PCEs according to the ever-increasing requirements of the concrete industry. Here, the bonding types generated between a PCE with silyl functionalities (PCE-Sil) and a synthetic calcium silicate hydrate (C-S-H) are analyzed using XRD, 29Si NMR spectroscopy, and synchrotron-based techniques, such as NEXAFS and EXAFS. The results indicated that the carboxylic groups present in PCE-Sil interact by a ligand-type bond with calcium, which modified not only the symmetry and coordination number of the calcium located at the surface of C-S-H but also the neighboring silicon atoms of the C-S-H. In addition, the silyl functionalities of the PCE-Sil generated covalent bonds through siloxane bridges between the silanol groups of PCE-Sil and the nonbonding oxygen located at the dimeric sites in C-S-H, forming new bridging silicon sites and subsequently increasing the silicate polymerization.

  11. Structural analysis of phospholipase A2 from functional perspective. 1. Functionally relevant solution structure and roles of the hydrogen-bonding network.

    Science.gov (United States)

    Yuan, C; Byeon, I J; Li, Y; Tsai, M D

    1999-03-09

    Bovine pancreatic phospholipase A2 (PLA2), a small (13.8 kDa) Ca2+-dependent lipolytic enzyme, is rich in functional and structural character. In an effort to examine its detailed structure-function relationship, we determined its solution structure by multidimensional nuclear magnetic resonance (NMR) spectroscopy at a functionally relevant pH. An ensemble of 20 structures generated has an average root-mean-square deviation (RMSD) of 0.62 +/- 0.08 A for backbone (N, Calpha, C) atoms and 0.98 +/- 0.09 A for all heavy atoms. The overall structure shows several notable differences from the crystal structure: the first three residues at the N-terminus, the calcium-binding loop (Y25-T36), and the surface loop (V63-N72) appear to be flexible; the alpha-helical conformation of helix B (E17-F22) is absent; helix D appears to be shorter (D59-V63 instead of D59-D66); and the hydrogen-bonding network is less defined. These differences were analyzed in relation to the function of PLA2. We then further examined the H-bonding network, because its functional role or even its existence in solution has been in dispute recently. Our results show that part of the H-bonding network (the portion away from N-terminus) clearly exists in solution, as evidenced by direct observation (at 11.1 ppm) of a strong H-bond between Y73 and D99 and an implicated interaction between D99 and H48. Analyses of a series of mutants indicated that the existence of the Y73.D99 H-bond correlates directly with the conformational stability of the mutant. Loss of this H-bond results in a loss of 2-3 kcal/mol in the conformational stability of PLA2. The unequivocal identification and demonstration of the structural importance of a specific hydrogen bond, and the magnitude of its contribution to conformational stability, are uncommon to the best of our knowledge. Our results also suggest that, while the D99.H48 catalytic diad is the key catalytic machinery of PLA2, it also helps to maintain conformational

  12. Soil eukaryotic functional diversity, a metatranscriptomic approach.

    Science.gov (United States)

    Bailly, Julie; Fraissinet-Tachet, Laurence; Verner, Marie-Christine; Debaud, Jean-Claude; Lemaire, Marc; Wésolowski-Louvel, Micheline; Marmeisse, Roland

    2007-11-01

    To appreciate the functional diversity of communities of soil eukaryotic micro-organisms we evaluated an experimental approach based on the construction and screening of a cDNA library using polyadenylated mRNA extracted from a forest soil. Such a library contains genes that are expressed by each of the different organisms forming the community and represents its metatranscriptome. The diversity of the organisms that contributed to this library was evaluated by sequencing a portion of the 18S rDNA gene amplified from either soil DNA or reverse-transcribed RNA. More than 70% of the sequences were from fungi and unicellular eukaryotes (protists) while the other most represented group was the metazoa. Calculation of richness estimators suggested that more than 180 species could be present in the soil samples studied. Sequencing of 119 cDNA identified genes with no homologues in databases (32%) and genes coding proteins involved in different biochemical and cellular processes. Surprisingly, the taxonomic distribution of the cDNA and of the 18S rDNA genes did not coincide, with a marked under-representation of the protists among the cDNA. Specific genes from such an environmental cDNA library could be isolated by expression in a heterologous microbial host, Saccharomyces cerevisiae. This is illustrated by the functional complementation of a histidine auxotrophic yeast mutant by two cDNA originating possibly from an ascomycete and a basidiomycete fungal species. Study of the metatranscriptome has the potential to uncover adaptations of whole microbial communities to local environmental conditions. It also gives access to an abundant source of genes of biotechnological interest.

  13. Particle Bonding Mechanism in Cold Gas Dynamic Spray: A Three-Dimensional Approach

    Science.gov (United States)

    Zhu, Lin; Jen, Tien-Chien; Pan, Yen-Ting; Chen, Hong-Sheng

    2017-12-01

    Cold gas dynamic spray (CGDS) is a surface coating process that uses highly accelerated particles to form the surface coating. In the CGDS process, metal particles with a diameter of 1-50 µm are carried by a gas stream at high pressure (typically 20-30 atm) through a de Laval-type nozzle to achieve supersonic velocity upon impact onto the substrate. Typically, the impact velocity ranges between 300 and 1200 m/s in the CGDS process. When the particle is accelerated to its critical velocity, which is defined as the minimum in-flight velocity at which it can deposit on the substrate, adiabatic shear instabilities will occur. Herein, to ascertain the critical velocities of different particle sizes on the bonding efficiency in CGDS process, three-dimensional numerical simulations of single particle deposition process were performed. In the CGDS process, one of the most important parameters which determine the bonding strength with the substrate is particle impact temperature. It is hypothesized that the particle will bond to the substrate when the particle's impacting velocity surpasses the critical velocity, at which the interface can achieve 60% of the melting temperature of the particle material (Ref 1, 2). Therefore, critical velocity should be a main parameter on the coating quality. Note that the particle critical velocity is determined not only by its size, but also by its material properties. This study numerically investigates the critical velocity for the particle deposition process in CGDS. In the present numerical analysis, copper (Cu) was chosen as particle material and aluminum (Al) as substrate material. The impacting velocities were selected between 300 and 800 m/s increasing in steps of 100 m/s. The simulation result reveals temporal and spatial interfacial temperature distribution and deformation between particle(s) and substrate. Finally, a comparison is carried out between the computed results and experimental data.

  14. Global and local approaches to population analysis: Bonding patterns in superheavy element compounds

    Science.gov (United States)

    Oleynichenko, Alexander; Zaitsevskii, Andréi; Romanov, Stepan; Skripnikov, Leonid V.; Titov, Anatoly V.

    2018-03-01

    Relativistic effective atomic configurations of superheavy elements Cn, Nh and Fl and their lighter homologues (Hg, Tl and Pb) in their simple compounds with fluorine and oxygen are determined using the analysis of local properties of molecular Kohn-Sham density matrices in the vicinity of heavy nuclei. The difference in populations of atomic spinors with the same orbital angular momentum and different total angular momenta is demonstrated to be essential for understanding the peculiarities of chemical bonding in superheavy element compounds. The results are fully compatible with those obtained by the relativistic iterative version of conventional projection analysis of global density matrices.

  15. Diffusion kinetics in aluminium–gold bond contacts from first-principles density functional calculations

    Czech Academy of Sciences Publication Activity Database

    Ulrich, C. M.; Hashibon, A.; Svoboda, Jiří; Elsässer, C.; Helm, D.; Riedel, H.

    2011-01-01

    Roč. 59, č. 20 (2011), s. 7634-7644 ISSN 1359-6454 R&D Projects: GA ČR GAP204/10/1784 Institutional research plan: CEZ:AV0Z20410507 Keywords : Bonding * Diffusion * Intermetallic compounds Subject RIV: BJ - Thermodynamics Impact factor: 3.755, year: 2011

  16. Adhesive Bonding and Corrosion Performance Investigated as a Function of Aluminum Oxide Chemistry and Adhesives

    NARCIS (Netherlands)

    Abrahami, S.T.; Hauffman, T.; de Kok, John M.M.; Terryn, H.A.; Mol, J.M.C.

    2017-01-01

    The long-term strength and durability of an adhesive bond is dependent on the stability of the oxide-adhesive interface. As such, changes in the chemistry of the oxide and/or the adhesive are expected to modify the interfacial properties and affect the joint performance in practice. The upcoming

  17. Functionalization of N2 to NH3 via direct N ≡ N bond cleavage ...

    Indian Academy of Sciences (India)

    rection (for Heptane, Toluene and THF) was performed using the polarized continuum model (PCM),54–56 nat- ural population analysis (NPA) was performed using same level of theory and basis set. A natural bond orbital analysis (NBO) was carried out to understand more about the electronic structure of the model sys-.

  18. X-ray Absorption Spectroscopy and Density Functional Theory Studies of [(H3buea)FeIII-X]n1 (X= S2-, O2-,OH-): Comparison of Bonding and Hydrogen Bonding in Oxo and Sulfido Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Dey, Abhishek; Hocking, Rosalie K.; /Stanford U., Chem. Dept.; Larsen, Peter; Borovik, Andrew S.; /Kansas U.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.; /SLAC,

    2006-09-27

    Iron L-edge, iron K-edge, and sulfur K-edge X-ray absorption spectroscopy was performed on a series of compounds [Fe{sup III}H{sub 3}buea(X)]{sup n-} (X = S{sup 2-}, O{sup 2-}, OH{sup -}). The experimentally determined electronic structures were used to correlate to density functional theory calculations. Calculations supported by the data were then used to compare the metal-ligand bonding and to evaluate the effects of H-bonding in Fe{sup III}-O vs Fe{sup III-}S complexes. It was found that the Fe{sup III-}O bond, while less covalent, is stronger than the FeIII-S bond. This dominantly reflects the larger ionic contribution to the Fe{sup III-}O bond. The H-bonding energy (for three H-bonds) was estimated to be -25 kcal/mol for the oxo as compared to -12 kcal/mol for the sulfide ligand. This difference is attributed to the larger charge density on the oxo ligand resulting from the lower covalency of the Fe-O bond. These results were extended to consider an Fe{sup IV-}O complex with the same ligand environment. It was found that hydrogen bonding to Fe{sup IV-}O is less energetically favorable than that to Fe{sup III-}O, which reflects the highly covalent nature of the Fe{sup IV-}O bond.

  19. New Approach to Conflicts within and between Belief Functions

    OpenAIRE

    Daniel, Milan

    2009-01-01

    This study deals with conflicts of belief functions. Internal conflicts of belief functions and conflicts between belief functions are described and analyzed here. Differences of belief functions are distinguished from conflicts between them. Three new different approaches to conflicts are presented: combinational, plausibility and comparative. The presented approaches to conflicts are compared to Liu's interpretation of conflicts.

  20. Effects of Bond Coating on NiCrBSi-Mo Composite Functional Coating Properties in Plasma Spraying NiCrBSi-Mo/Ni Coating

    OpenAIRE

    DU Ji-yu; LI Fang-yi; LU Hai-yang; SHANG Jian-tong; LI Zhen

    2017-01-01

    Nickel-based bond coating and composite functional coating were sprayed on leaf blade steel material FV520B successively by using air plasma spraying system. NiCrBSi-Mo powder deposition rate, coating porosity, bonding strength and surface hardness were tested. The results indicate that, for the NiCrBSi-Mo/Ni coating, bond coating with 180-220μm thickness can improve NiCrBSi-Mo powder deposition rate while the surface coating with lower porosity, higher bonding strength and high hardness is p...

  1. Effects of density functionals and dispersion interactions on geometries, bond energies and harmonic frequencies of Etbnd UX3 (E = N, P, CH; X = H, F, Cl)

    Science.gov (United States)

    Pandey, Krishna Kumar; Patidar, Pankaj; Patidar, Sunil Kumar; Vishwakarma, Ravi

    2014-12-01

    Quantum-chemical calculations have been performed to evaluate the geometries, bonding nature and harmonic frequencies of the compounds [Etbnd UX3] at DFT, DFT-D3, DFT-D3(BJ) and DFT-dDSc levels using different density functionals BP86, BLYP, PBE, revPBE, PW91, TPSS and M06-L. The stretching frequency of Utbnd N bond in [Ntbnd UF3] calculated with DFT/BLYP closely resembles with the experimental value. The performance of different density functionals for accurate Utbnd N vibrational frequencies follows the order BLYP > revPBE > BP86 > PW91 > TPSS > PBE > M06-L. The BLYP functional gives accurate value of the Utbnd E bond distances. The uranium atom in the studied compounds [Etbnd UX3] is positively charged. Upon going from [Etbnd UF3] to [Etbnd UCl3], the partial Hirshfeld charge on uranium atom decreases because of the lower electronegativity of chlorine compared to flourine. The Gopinathan-Jug bond order for Utbnd E bonds ranges from 2.90 to 3.29. The Utbnd E bond dissociation energies vary with different density functionals as M06-L < TPSS < BLYP < revPBE < BP86 < PBE ≈ PW91. The orbital interactions ΔEorb, in all studied compounds [Etbnd UX3] are larger than the electrostatic interaction ΔEelstat, which means the Utbnd N bonds in these compound have greater degree of covalent character (in the range 63.8-77.2%). The Usbnd E σ-bonding interaction is the dominant bonding interaction in the nitride and methylidyne complexes while it is weaker in [Ptbnd UX3]. The dispersion energy contributions to the total bond dissociation energies are rather small. Compared to the Grimme's D3(BJ) corrections, the Corminboeuf's dispersion corrections are larger with metaGGA functionals (TPSS, M06-L) while smaller with GGA functionals.

  2. Approaches toward functional fluid supported lipid bilayers

    Science.gov (United States)

    Weng, Kevin Chun-I.

    Planar supported lipid bilayers (PSLBs) have attracted immense interest for their properties as model cell membranes and for potential applications in biosensors and lab-on-a-chip devices. Our study covers three aspects of the construction, characterization, and application of functional PSLBs. First, a combination of micro-fabrication, the Langmuir-Blodgett (LB) technique, and fusion of extruded small unilamellar vesicle (E-SUVs) in sequence was used to create polymer-cushioned PSLBs in a microarray format. Random lipo-glycocopolymer mixed with L-alpha-phosphatidylcholine (egg PC) was compressed at the air-water interface and transferred onto the photoresist-patterned substrate by the LB technique to achieve spatially directed deposition. Construction of planar bilayers in an aqueous environment was subsequently completed by vesicle fusion. Epifluorescence microscopy, fluorescence recovery after photobleaching (FRAP), and electrophoresis-relaxation were employed to examine the resulting patterns as well as to verify the two-dimensional mobility of the supported membrane systems. This approach could possibly provide a useful route to create functional arrays of polymer-supported lipid bilayers. Second, we report the formation of fluid planar biomembranes on hydrophilic silica aerogels and xerogels. When the aerogel/xerogel was pre-hydrated and then allowed to incubate in egg PC E-SUV solution, lipid bilayers were formed due to the favorable interaction of vesicles with the hydroxyl-abundant silica surface. FRAP was used to determine the lateral diffusivity of membranes on aerogels. Quartz crystal microbalance with dissipation monitoring (QCM-D) was used to monitor the kinetics of the irreversible adsorption and fusion of vesicles into bilayers on xerogel thin films. Finally, we compared the formation of PSLBs with and without incorporation of monosialoganglioside GM1 (GM1) as the antigen for in situ antibody binding. Quantifiable differences were observed in the

  3. Bonding titanium on multi-walled carbon nanotubes for hydrogen storage: An electrochemical approach

    Energy Technology Data Exchange (ETDEWEB)

    Brieno-Enriquez, K.M.; Ledesma-Garcia, J. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, S.C., Parque Tecnologico Queretaro-Sanfandila, Pedro Escobedo, Qro, C.P. 76703 (Mexico); Perez-Bueno, J.J., E-mail: jperez@cideteq.mx [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, S.C., Parque Tecnologico Queretaro-Sanfandila, Pedro Escobedo, Qro, C.P. 76703 (Mexico); Godinez, Luis A. [Centro de Investigacion y Desarrollo Tecnologico en Electroquimica, S.C., Parque Tecnologico Queretaro-Sanfandila, Pedro Escobedo, Qro, C.P. 76703 (Mexico); Terrones, H. [Instituto Potosino de Investigacion Cientifica y Tecnologica, Division de Materiales Avanzados, Camino a la Presa San Jose 2055, Col. Lomas 4o Seccion C.P. 78216, San Luis Potosi (Mexico); Angeles-Chavez, C. [Instituto Mexicano del Petroleo, Programa de Ingenieria Molecular, Eje Central Lazaro Cardenas 152, A.P. 14-805, 07730 Mexico D.F. (Mexico)

    2009-06-15

    This work explores the use of some procedures, involving electrochemistry, in order to bond atomic Ti on the outer surface of multi-walled carbon nanotubes (MWNTs). It is assumed that each titanium atom has the potential of host up to four hydrogen molecules and relinquish them by heated. As a way to spread and stick nanotubes on an electrode, a tested route was drying a solution with nanotubes on a glassy carbon flat electrode. The MWNTs were treated by anodic polarization in organic media. Dichloromethane was selected as the medium and titanium tetrachloride as the precursor for attaching atomic Ti onto the nanotubes. The hydrogen adsorption, estimated from voltamperometry was five times higher on Ti-MWNTs that on bare nanotubes. The use of anodic polarization during the preparation of Ti-MWNTs may represent great significance in procedure, which was manifest during the voltamperometric evaluation of samples.

  4. Introducing Linear Functions: An Alternative Statistical Approach

    Science.gov (United States)

    Nolan, Caroline; Herbert, Sandra

    2015-01-01

    The introduction of linear functions is the turning point where many students decide if mathematics is useful or not. This means the role of parameters and variables in linear functions could be considered to be "threshold concepts". There is recognition that linear functions can be taught in context through the exploration of linear…

  5. Mechatronics by bond graphs an object-oriented approach to modelling and simulation

    CERN Document Server

    Damić, Vjekoslav

    2015-01-01

    This book presents a computer-aided approach to the design of mechatronic systems. Its subject is an integrated modeling and simulation in a visual computer environment. Since the first edition, the simulation software changed enormously, became more user-friendly and easier to use. Therefore, a second edition became necessary taking these improvements into account. The modeling is based on system top-down and bottom-up approach. The mathematical models are generated in a form of differential-algebraic equations and solved using numerical and symbolic algebra methods. The integrated approach developed is applied to mechanical, electrical and control systems, multibody dynamics, and continuous systems. .

  6. Functional approaches in translation studies in Germany Functional approaches in translation studies in Germany

    Directory of Open Access Journals (Sweden)

    Paul Kussmaul

    2008-04-01

    Full Text Available In the early phase of translation studies in Germany, contrastive linguistics played a major role. I shall briefly describe this approach so that the functional approach will become clearer by contrast. Influenced by the representatives of stylistique comparée, Vinay/Darbelnet (1968 Wolfram Wilss, for instance, in his early work (1971, 1977 makes frequent use of the notion transposition (German “Ausdrucksverschiebung“, cf. also Catford’s (1965 term shift. As a whole, of course, Wilss’ work has a much broader scope. More recently, he has investigated the role of cognition (1988 and the various factors in translator behaviour (1996. Nevertheless, transposition is still a very important and useful notion in describing the translation process. The need for transpositions arises when there is no possibility of formal one-to-one correspondence between source and target-language structures. The basic idea is that whenever there is a need for transposition, we are faced with a translation problem. In the early phase of translation studies in Germany, contrastive linguistics played a major role. I shall briefly describe this approach so that the functional approach will become clearer by contrast. Influenced by the representatives of stylistique comparée, Vinay/Darbelnet (1968 Wolfram Wilss, for instance, in his early work (1971, 1977 makes frequent use of the notion transposition (German “Ausdrucksverschiebung“, cf. also Catford’s (1965 term shift. As a whole, of course, Wilss’ work has a much broader scope. More recently, he has investigated the role of cognition (1988 and the various factors in translator behaviour (1996. Nevertheless, transposition is still a very important and useful notion in describing the translation process. The need for transpositions arises when there is no possibility of formal one-to-one correspondence between source and target-language structures. The basic idea is that whenever there is a need for

  7. Revisiting the European sovereign bonds with a permutation-information-theory approach

    Science.gov (United States)

    Fernández Bariviera, Aurelio; Zunino, Luciano; Guercio, María Belén; Martinez, Lisana B.; Rosso, Osvaldo A.

    2013-12-01

    In this paper we study the evolution of the informational efficiency in its weak form for seventeen European sovereign bonds time series. We aim to assess the impact of two specific economic situations in the hypothetical random behavior of these time series: the establishment of a common currency and a wide and deep financial crisis. In order to evaluate the informational efficiency we use permutation quantifiers derived from information theory. Specifically, time series are ranked according to two metrics that measure the intrinsic structure of their correlations: permutation entropy and permutation statistical complexity. These measures provide the rectangular coordinates of the complexity-entropy causality plane; the planar location of the time series in this representation space reveals the degree of informational efficiency. According to our results, the currency union contributed to homogenize the stochastic characteristics of the time series and produced synchronization in the random behavior of them. Additionally, the 2008 financial crisis uncovered differences within the apparently homogeneous European sovereign markets and revealed country-specific characteristics that were partially hidden during the monetary union heyday.

  8. A systemic approach for modeling soil functions

    Science.gov (United States)

    Vogel, Hans-Jörg; Bartke, Stephan; Daedlow, Katrin; Helming, Katharina; Kögel-Knabner, Ingrid; Lang, Birgit; Rabot, Eva; Russell, David; Stößel, Bastian; Weller, Ulrich; Wiesmeier, Martin; Wollschläger, Ute

    2018-03-01

    The central importance of soil for the functioning of terrestrial systems is increasingly recognized. Critically relevant for water quality, climate control, nutrient cycling and biodiversity, soil provides more functions than just the basis for agricultural production. Nowadays, soil is increasingly under pressure as a limited resource for the production of food, energy and raw materials. This has led to an increasing demand for concepts assessing soil functions so that they can be adequately considered in decision-making aimed at sustainable soil management. The various soil science disciplines have progressively developed highly sophisticated methods to explore the multitude of physical, chemical and biological processes in soil. It is not obvious, however, how the steadily improving insight into soil processes may contribute to the evaluation of soil functions. Here, we present to a new systemic modeling framework that allows for a consistent coupling between reductionist yet observable indicators for soil functions with detailed process understanding. It is based on the mechanistic relationships between soil functional attributes, each explained by a network of interacting processes as derived from scientific evidence. The non-linear character of these interactions produces stability and resilience of soil with respect to functional characteristics. We anticipate that this new conceptional framework will integrate the various soil science disciplines and help identify important future research questions at the interface between disciplines. It allows the overwhelming complexity of soil systems to be adequately coped with and paves the way for steadily improving our capability to assess soil functions based on scientific understanding.

  9. Bilocal functional approach to dynamical symmetry breaking

    International Nuclear Information System (INIS)

    Ebert, D.; Pervushin, V.N.

    1977-01-01

    The Abelian gauge theory of massless fermions (''quarks'') interacting with a massless neutral vector (''gluon'') field is considered. The Green two-particle functions of the quarks and vector gluons are computed. The graphical expression of the bilocal propagator and that of different terms in the expansion of path integrals for these functions are given

  10. Tertiary-Alcohol-Directed Functionalization of Remote C(sp3)-H Bonds by Sequential Hydrogen Atom and Heteroaryl Migrations.

    Science.gov (United States)

    Wu, Xinxin; Wang, Mingyang; Huan, Leitao; Wang, Dongping; Wang, Jinwei; Zhu, Chen

    2018-02-05

    Reported for the first time is a tertiary-alcohol-guided heteroarylation of remote C(sp 3 )-H bonds. The mild and direct generation of alkoxyl radicals from alcohols is enabled by visible-light photocatalysis. A remote hydrogen atom and heteroaryl migration sequence are involved in the reaction. Many sensitive groups remain intact in the reaction, thus illustrating wide functional-group compatibility. This protocol provides a practical strategy for the late-stage modification of alkyl ketones. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Effective bond orders from two-step spin-orbit coupling approaches: the I2, At2, IO(+), and AtO(+) case studies.

    Science.gov (United States)

    Maurice, Rémi; Réal, Florent; Gomes, André Severo Pereira; Vallet, Valérie; Montavon, Gilles; Galland, Nicolas

    2015-03-07

    The nature of chemical bonds in heavy main-group diatomics is discussed from the viewpoint of effective bond orders, which are computed from spin-orbit wave functions resulting from spin-orbit configuration interaction calculations. The reliability of the relativistic correlated wave functions obtained in such two-step spin-orbit coupling frameworks is assessed by benchmark studies of the spectroscopic constants with respect to either experimental data, or state-of-the-art fully relativistic correlated calculations. The I2, At2, IO(+), and AtO(+) species are considered, and differences and similarities between the astatine and iodine elements are highlighted. In particular, we demonstrate that spin-orbit coupling weakens the covalent character of the bond in At2 even more than electron correlation, making the consideration of spin-orbit coupling compulsory for discussing chemical bonding in heavy (6p) main group element systems.

  12. Influence of NaOCl deproteinization on shear bond strength in function of dentin depth.

    Science.gov (United States)

    Toledano, Manuel; Perdigão, Jorge; Osorio, Estrella; Osorio, Raquel

    2002-08-01

    To determine the influence of NaOCl application on shear bond strengths (SBS) to superficial and deep dentin, using Prime & Bond 2.1. Superficial and deep dentin was exposed in 40 extracted third molars by sectioning the occlusal surface immediately under the enamel-dentin junction or close to the pulp chamber. After polishing the dentin disks (600-grit SiC), they were assigned to two groups: (1) 36% orthophosphoric acid for 15 seconds, or (2): 36% orthophosphoric acid for 15 seconds followed by 5% sodium hypochlorite (NaOCl) for 2 minutes. The dentin adhesive was applied as per manufacturer's instructions, followed by TPH resin-based composite. The specimens were stored in water for 24 hours at 37 degrees C and thermocycled x500 and SBS were determined. Data were statistically analyzed with ANOVA and Student's t-test. For acid-etched specimens, superficial dentin resulted in statistically higher mean SBS than deep dentin. After NaOCl application, deep and superficial dentin resulted in statistically similar mean SBS. Collagen removal did not affect mean SBS on superficial dentin, while SBS values on deep dentin were increased.

  13. New approaches to organocatalysis based on C–H and C–X bonding for electrophilic substrate activation

    Directory of Open Access Journals (Sweden)

    Pavel Nagorny

    2016-12-01

    Full Text Available Hydrogen bond donor catalysis represents a rapidly growing subfield of organocatalysis. While traditional hydrogen bond donors containing N–H and O–H moieties have been effectively used for electrophile activation, activation based on other types of non-covalent interactions is less common. This mini review highlights recent progress in developing and exploring new organic catalysts for electrophile activation through the formation of C–H hydrogen bonds and C–X halogen bonds.

  14. Multiconfigurational Green's function approaches in quantum chemistry

    International Nuclear Information System (INIS)

    Yeager, D.L.

    1984-01-01

    The author discusses multiconfigurational Green's function techniques and generalizations. In particular he is interested in developing and applying these techniques for isolated atoms and small molecules. Furthermore, he develops formalisms that are fairly clear, accurate, and capable of being applied to open-shell and highly-correlated systems as well as to closed-shell systems with little electronic correlation. The two kinds of Green's functions that this article discusses are the single-particle Green's function and the retarded two-time Green's function in the energy representation. The poles of the former give the ionization potentials and electron affinities while the poles of the latter give the excitation energies. The multiconfigurational approximations are known as the multiconfigurational electron propagator (MCEP) and the multiconfigurational time-dependent Hartree-Fock (MCTDHF) (also known as the multiconfigurational random phase approximation (MCRPA) or the multiconfigurational linear response), respectively. 44 references

  15. Mechatronic modeling of a 750kW fixed-speed wind energy conversion system using the Bond Graph Approach.

    Science.gov (United States)

    Khaouch, Zakaria; Zekraoui, Mustapha; Bengourram, Jamaa; Kouider, Nourreeddine; Mabrouki, Mustapha

    2016-11-01

    In this paper, we would like to focus on modeling main parts of the wind turbines (blades, gearbox, tower, generator and pitching system) from a mechatronics viewpoint using the Bond-Graph Approach (BGA). Then, these parts are combined together in order to simulate the complete system. Moreover, the real dynamic behavior of the wind turbine is taken into account and with the new model; final load simulation is more realistic offering benefits and reliable system performance. This model can be used to develop control algorithms to reduce fatigue loads and enhance power production. Different simulations are carried-out in order to validate the proposed wind turbine model, using real data provided in the open literature (blade profile and gearbox parameters for a 750 kW wind turbine). Copyright © 2016 ISA. Published by Elsevier Ltd. All rights reserved.

  16. Designing Homogeneous Bromine Redox Catalysis for Selective Aliphatic C-H Bond Functionalization.

    Science.gov (United States)

    Muniz, Kilian; Becker, Peter; Duhamel, Thomas; Martinez, Claudio

    2018-02-27

    The potential of homogeneous oxidation catalysis employing bromine has remained largely unexplored. The combination of tetraalkylammonium bromide and 3-chloroperbenzoic acid offers a unique catalyst system for the convenient and selective oxidation of saturated Csp3-H bonds upon photochemical initiation with visible light. It enables remote intramolecular, position-selective C-H amination as demonstrated for 20 different examples. For the first time, a N-halogenated intermediate could be isolated as the active catalyst state in a catalytic Hofmann-Löffler reaction. In addition, a novel expeditious one-pot synthesis of N-sulfonyloxaziridines from N-sulfonamides was developed and exemplified for 15 transformations. These pioneering examples provide a change in paradigm for molecular catalysis with bromine. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Integral equations of hadronic correlation functions a functional- bootstrap approach

    CERN Document Server

    Manesis, E K

    1974-01-01

    A reasonable 'microscopic' foundation of the Feynman hadron-liquid analogy is offered, based on a class of models for hadron production. In an external field formalism, the equivalence (complementarity) of the exclusive and inclusive descriptions of hadronic reactions is specifically expressed in a functional-bootstrap form, and integral equations between inclusive and exclusive correlation functions are derived. Using the latest CERN-ISR data on the two-pion inclusive correlation function, and assuming rapidity translational invariance for the exclusive one, the simplest integral equation is solved in the 'central region' and an exclusive correlation length in rapidity predicted. An explanation is also offered for the unexpected similarity observed between pi /sup +/ pi /sup -/ and pi /sup -/ pi /sup -/ inclusive correlations. (31 refs).

  18. Functional renormalization group approach to neutron matter

    Directory of Open Access Journals (Sweden)

    Matthias Drews

    2014-11-01

    Full Text Available The chiral nucleon-meson model, previously applied to systems with equal number of neutrons and protons, is extended to asymmetric nuclear matter. Fluctuations are included in the framework of the functional renormalization group. The equation of state for pure neutron matter is studied and compared to recent advanced many-body calculations. The chiral condensate in neutron matter is computed as a function of baryon density. It is found that, once fluctuations are incorporated, the chiral restoration transition for pure neutron matter is shifted to high densities, much beyond three times the density of normal nuclear matter.

  19. Bond breaking and bond making in tetraoxygen: analysis of the O2(X3Sigma(g)-) + O2(X3Sigma(g)-) O4 reaction using the electron pair localization function.

    Science.gov (United States)

    Scemama, Anthony; Caffarel, Michel; Ramírez-Solís, Alejandro

    2009-08-06

    We study the nature of the electron pairing at the most important critical points of the singlet potential energy surface of the 2O2 O4 reaction and its evolution along the reaction coordinate using the electron pair localization function (EPLF) [Scemama, A.; Chaquin, P.; Caffarel, M. J. Chem. Phys. 2004, 121, 1725]. To do that, the 3D topology of the EPLF calculated with quantum Monte Carlo (at both variational and fixed-node-diffusion Monte Carlo levels) using Hartree-Fock, multiconfigurational CASSCF, and explicitly correlated trial wave functions is analyzed. At the O4 equilibrium geometry the EPLF analysis reveals four equivalent covalent bonds and two lone pairs on each oxygen atom. Along the reaction path toward dissociation it is found that the two oxygen-oxygen bonds are not broken simultaneously but sequentially, and then the lone pairs are rearranged. In a more general perspective, the usefulness of the EPLF as a unique tool to analyze the topology of electron pairing in nontrivial chemical bonding situations as well as to visualize the major steps involved in chemical reactivity is emphasized. In contrast with most standard schemes to reveal electron localization (atoms in molecules, electron localization function, natural bond orbital, etc.), the newly introduced EPLF function gives a direct access to electron pairings in molecules.

  20. An estimating function approach to linkage heterogeneity

    Indian Academy of Sciences (India)

    X chromosome. Science 230, 753–758. Fujii Y. 1994 On homogeneity test using estimating function. Bull. Informat. Cybern. 26, 101–107. Grice D. E., Halmi K. A., Fichter M. M., Strober M., Woodside. D. B., Treasure J. T. et al. 2002 Evidence for a susceptibility gene for anorexia nervosa on chromosome 1. Am. J. Hum. Genet.

  1. Realistic representation of grain shapes in CFD-DEM simulations of sediment transport with a bonded-sphere approach

    Science.gov (United States)

    Sun, Rui; Xiao, Heng; Sun, Honglei

    2017-09-01

    Development of algorithms and growth of computational resources in the past decades have enabled simulations of sediment transport processes with unprecedented fidelities. The Computational Fluid Dynamics-Discrete Element Method (CFD-DEM) is one of the high-fidelity approaches, where the motions of and collisions among the sediment grains as well as their interactions with surrounding fluids are resolved. In most DEM solvers the particles are modeled as soft spheres due to computational efficiency and implementation complexity considerations, although natural sediments are usually a mixture of non-spherical (e.g., disk-, blade-, and rod-shaped) particles. Previous attempts to extend sphere-based DEM to treat irregular particles neglected fluid-induced torques on particles, and the method lacked flexibility to handle sediments with an arbitrary mixture of particle shapes. In this contribution we proposed a simple, efficient approach to representing common sediment grain shapes with bonded spheres, where the fluid forces are computed and applied on each sphere. The proposed approach overcomes the aforementioned limitations of existing methods and has improved efficiency and flexibility over existing approaches. We use numerical simulations to demonstrate the merits and capability of the proposed method in predicting the falling characteristics, terminal velocity, threshold of incipient motion, and transport rate of natural sediments. The simulations show that the proposed method is a promising approach for faithful representation of natural sediment, which leads to accurate simulations of their transport dynamics. While this work focuses on non-cohesive sediments, the proposed method also opens the possibility for first-principle-based simulations of the flocculation and sedimentation dynamics of cohesive sediments. Elucidation of these physical mechanisms can provide much needed improvement on the prediction capability and physical understanding of muddy coast

  2. Enhanced dispersion stability and mobility of carboxyl-functionalized carbon nanotubes in aqueous solutions through strong hydrogen bonds

    International Nuclear Information System (INIS)

    Bahk, Yeon Kyoung; He, Xu; Gitsis, Emmanouil; Kuo, Yu-Ying; Kim, Nayoung; Wang, Jing

    2015-01-01

    Dispersion of carbon nanotubes has been heavily studied due to its importance for their technical applications, toxic effects, and environmental impacts. Common electrolytes, such as sodium chloride and potassium chloride, promote agglomeration of nanoparticles in aqueous solutions. On the contrary, we discovered that acetic electrolytes enhanced the dispersion of multi-walled carbon nanotubes (MWCNTs) with carboxyl functional group through the strong hydrogen bond, which was confirmed by UV–Vis spectrometry, dispersion observations and aerosolization-quantification method. When concentrations of acetate electrolytes such as ammonium acetate (CH 3 CO 2 NH 4 ) and sodium acetate (CH 3 CO 2 Na) were lower than 0.03 mol per liter, MWCNT suspensions showed better dispersion and had higher mobility in porous media. The effects by the acetic environment are also applicable to other nanoparticles with the carboxyl functional group, which was demonstrated with polystyrene latex particles as an example

  3. Functional RG approach to the Potts model

    Science.gov (United States)

    Ben Alì Zinati, Riccardo; Codello, Alessandro

    2018-01-01

    The critical behavior of the (n+1) -states Potts model in d-dimensions is studied with functional renormalization group techniques. We devise a general method to derive β-functions for continuous values of d and n and we write the flow equation for the effective potential (LPA’) when instead n is fixed. We calculate several critical exponents, which are found to be in good agreement with Monte Carlo simulations and ɛ-expansion results available in the literature. In particular, we focus on Percolation (n\\to0) and Spanning Forest (n\\to-1) which are the only non-trivial universality classes in d  =  4,5 and where our methods converge faster.

  4. Green's function approach to neutron flux discontinuities

    International Nuclear Information System (INIS)

    Saad, E.A.; El-Wakil, S.A.

    1980-01-01

    The present work is devoted to the presentation of analytical method for the calculation of elastically and inelastically slowed down neutrons in an infinite non-absorbing medium. On the basis of the central limit theory (CLT) and the integral transform technique the slowing down equation including inelastic scattering, in terms of the Green function of elastic scattering, is solved. The Green function is decomposed according to the number of collisions. Placzec discontinuity associated with elastic scattering in addition to two discontinuities due to inelastic scattering are investigated. Numerical calculations for Fe 56 show that the elastic discontinuity produces about 41.8% change in the collision density whilst the ratio of the inelastic collision density discontinuity at qsub(o)sup(+) to the Placzec discontinuity at usub(o) + 1n 1/oc gives 55.7 percent change. (author)

  5. Using the critical design approach for rethinking citizens’ emotional bond with urban spaces

    Directory of Open Access Journals (Sweden)

    A. Matassa

    2015-12-01

    Full Text Available This paper focuses on the use of the critical design approach to analyze and understand the connection between human beings and urban spaces. Taking inspiration from the value that place and space have for people (e.g. for the construction of their individual identities and from previous works concerning memories in the urban space experienced while cycling, we propose to undertake a design research where ambiguous and cognitively dissonant messages are delivered through a wearable device to encourage individuals to rethink and revalue their relations with space, consequently reshaping their personal identity.

  6. Nickel-Catalyzed C–O Bond-Cleaving Alkylation of Esters: Direct Replacement of the Ester Moiety by Functionalized Alkyl Chains

    KAUST Repository

    Liu, Xiangqian

    2017-06-07

    Two efficient protocols for the nickel-catalyzed aryl–alkyl cross-coupling reactions using esters as coupling components have been established. The methods enable the selective oxidative addition of nickel to acyl C–O and aryl C–O bonds and allow the aryl–alkyl cross-coupling via decarbonylative bond cleavage or through cleavage of a C–O bond with high efficiency and good functional group compatibility. The protocols allow the streamlined, unconventional utilization of widespread ester groups and their precursors, carboxylic acids and phenols, in synthetic organic chemistry.

  7. A Constructive Sharp Approach to Functional Quantization of Stochastic Processes

    OpenAIRE

    Junglen, Stefan; Luschgy, Harald

    2010-01-01

    We present a constructive approach to the functional quantization problem of stochastic processes, with an emphasis on Gaussian processes. The approach is constructive, since we reduce the infinite-dimensional functional quantization problem to a finite-dimensional quantization problem that can be solved numerically. Our approach achieves the sharp rate of the minimal quantization error and can be used to quantize the path space for Gaussian processes and also, for example, Lévy processes.

  8. Atoms in Valence Bond – AiVB : synopsis and test results

    NARCIS (Netherlands)

    Zielinski, M.L.; van Lenthe, J.H.

    2010-01-01

    The Atoms in Valence Bond (AiVB) method, a new approach in the Valence Bond, is introduced. This approach combines the ideas behind the early Atoms in Molecules (AIM) developments, e.g. by Moffit [21], to understand a molecular wave function in terms of proper atomic wave functions, with the

  9. Functionalization of N 2 to NH 3 via direct N≡ N bond cleavage ...

    Indian Academy of Sciences (India)

    Atmospheric N2 can be cleaved directly to yield metal-nitride (before proceeding to the functionalization of N of coordinated N2) and subsequently functionalized to ammonia using M(III)(NMe2)3 (M = W/Mo) as a catalyst, and suitable proton and electron sources. The calculated energies of thermodynamic and kinetic ...

  10. Longitudinal associations between parental bonding, parenting stress, and executive functioning in toddlerhood

    NARCIS (Netherlands)

    De Cock, E.S.A.; Henrichs, J.; Klimstra, T.A.; Maas, A.J.B.M.; Vreeswijk, C.M.J.M.; Meeus, W.H.J.; Van Bakel, H.J.A.

    Early executive functioning is an important predictor for future development of children’s cognitive skills and behavioral outcomes. Parenting behavior has proven to be a key environmental determinant of child executive functioning. However, the association of parental affect and cognitions directed

  11. Longitudinal Associations Between Parental Bonding, Parenting Stress, and Executive Functioning in Toddlerhood

    NARCIS (Netherlands)

    de Cock, Evi S.A.; Henrichs, Jens; Klimstra, Theo A.; Janneke, A.; Vreeswijk, Charlotte M.J.M.; Meeus, Wim H.J.; van Bakel, Hedwig J.A.

    2017-01-01

    Early executive functioning is an important predictor for future development of children’s cognitive skills and behavioral outcomes. Parenting behavior has proven to be a key environmental determinant of child executive functioning. However, the association of parental affect and cognitions directed

  12. A Multivariate Approach to Functional Neuro Modeling

    DEFF Research Database (Denmark)

    Mørch, Niels J.S.

    1998-01-01

    by the application of linear and more flexible, nonlinear microscopic regression models to a real-world dataset. The dependency of model performance, as quantified by generalization error, on model flexibility and training set size is demonstrated, leading to the important realization that no uniformly optimal model......, provides the basis for a generalization theoretical framework relating model performance to model complexity and dataset size. Briefly summarized the major topics discussed in the thesis include: - An introduction of the representation of functional datasets by pairs of neuronal activity patterns...... exists. - Model visualization and interpretation techniques. The simplicity of this task for linear models contrasts the difficulties involved when dealing with nonlinear models. Finally, a visualization technique for nonlinear models is proposed. A single observation emerges from the thesis...

  13. Deflection control of functionally graded material beams with bonded piezoelectric sensors and actuators

    International Nuclear Information System (INIS)

    Gharib, Ahmad; Salehi, Manouchehr; Fazeli, Saeed

    2008-01-01

    An analytical solution is developed for analysis of functionally graded material (FGM) beams containing two layers of piezoelectric material, used as sensor and actuator. The properties of FGM layer are functionally graded in the thickness direction according to the volume fraction power law distribution. The equations of motion are derived by using Hamilton's principle, based on the first-order shear deformation theory. By using a displacement potential function, and assumption of harmonic vibration, the equations of motion have been solved analytically. Finally, the effects of FGM constituent volume fraction in the peak responses for various volume fraction indexes have been graphically illustrated

  14. Quantum mechanical facets of chemical bonds

    International Nuclear Information System (INIS)

    Daudel, R.

    1976-01-01

    To define the concept of bond is both a central problem of quantum chemistry and a difficult one. The concept of bond appeared little by little in the mind of chemists from empirical observations. From the wave-mechanical viewpoint it is not an observable. Therefore there is no precise operator associated with that concept. As a consequence there is not a unique approach to the idea of chemical bond. This is why it is preferred to present various quantum mechanical facets, e.g. the energetic facet, the density facet, the partitioning facet and the functional facet, of that important concept. (Auth.)

  15. Toward Intelligent Hemodynamic Monitoring: A Functional Approach

    Directory of Open Access Journals (Sweden)

    Pierre Squara

    2012-01-01

    Full Text Available Technology is now available to allow a complete haemodynamic analysis; however this is only used in a small proportion of patients and seems to occur when the medical staff have the time and inclination. As a result of this, significant delays occur between an event, its diagnosis and therefore, any treatment required. We can speculate that we should be able to collect enough real time information to make a complete, real time, haemodynamic diagnosis in all critically ill patients. This article advocates for “intelligent haemodynamic monitoring”. Following the steps of a functional analysis, we answered six basic questions. (1 What is the actual best theoretical model for describing haemodynamic disorders? (2 What are the needed and necessary input/output data for describing this model? (3 What are the specific quality criteria and tolerances for collecting each input variable? (4 Based on these criteria, what are the validated available technologies for monitoring each input variable, continuously, real time, and if possible non-invasively? (5 How can we integrate all the needed reliably monitored input variables into the same system for continuously describing the global haemodynamic model? (6 Is it possible to implement this global model into intelligent programs that are able to differentiate clinically relevant changes as opposed to artificial changes and to display intelligent messages and/or diagnoses?

  16. A probabilistic approach to delineating functional brain regions

    DEFF Research Database (Denmark)

    Kalbitzer, Jan; Svarer, Claus; Frokjaer, Vibe G

    2009-01-01

    The purpose of this study was to develop a reliable observer-independent approach to delineating volumes of interest (VOIs) for functional brain regions that are not identifiable on structural MR images. The case is made for the raphe nuclei, a collection of nuclei situated in the brain stem known......-independent, reliable approach to delineating regions that can be identified only by functional imaging, here exemplified by the raphe nuclei. This approach can be used in future studies to create functional VOI maps based on neuroreceptor fingerprints retrieved through in vivo brain imaging Udgivelsesdato: 2009/6...

  17. The Specific Role of Childhood Abuse, Parental Bonding, and Family Functioning in Female Adolescents With Borderline Personality Disorder.

    Science.gov (United States)

    Infurna, Maria Rita; Brunner, Romuald; Holz, Birger; Parzer, Peter; Giannone, Francesca; Reichl, Corinna; Fischer, Gloria; Resch, Franz; Kaess, Michael

    2016-04-01

    This study examined a broad variety of adverse childhood experiences in a consecutive sample of female adolescent inpatients with borderline personality disorder (BPD; n = 44) compared with a clinical control (CC; n = 47) group with mixed psychiatric diagnoses. BPD was diagnosed using a structured clinical interview; different dimensions of childhood adversity were assessed using the Childhood Experiences of Care and Abuse Questionnaire, the Parental Bonding Instrument, and the Family Assessment Device. A history of childhood adversity was significantly more common in patients with BPD than in the CC group. Using a multivariate model, sexual abuse (OR = 13.8), general family functioning (OR = 8.9), and low maternal care (OR = 7.6) were specific and independent predictors of adolescent BPD. The results increase our knowledge of the specific role of different dimensions of childhood adversity in adolescent BPD. They have important implications for prevention and early intervention as they highlight the need for specific strategies for involving the family.

  18. A promising tool to achieve chemical accuracy for density functional theory calculations on Y-NO homolysis bond dissociation energies.

    Science.gov (United States)

    Li, Hong Zhi; Hu, Li Hong; Tao, Wei; Gao, Ting; Li, Hui; Lu, Ying Hua; Su, Zhong Min

    2012-01-01

    A DFT-SOFM-RBFNN method is proposed to improve the accuracy of DFT calculations on Y-NO (Y = C, N, O, S) homolysis bond dissociation energies (BDE) by combining density functional theory (DFT) and artificial intelligence/machine learning methods, which consist of self-organizing feature mapping neural networks (SOFMNN) and radial basis function neural networks (RBFNN). A descriptor refinement step including SOFMNN clustering analysis and correlation analysis is implemented. The SOFMNN clustering analysis is applied to classify descriptors, and the representative descriptors in the groups are selected as neural network inputs according to their closeness to the experimental values through correlation analysis. Redundant descriptors and intuitively biased choices of descriptors can be avoided by this newly introduced step. Using RBFNN calculation with the selected descriptors, chemical accuracy (≤1 kcal·mol(-1)) is achieved for all 92 calculated organic Y-NO homolysis BDE calculated by DFT-B3LYP, and the mean absolute deviations (MADs) of the B3LYP/6-31G(d) and B3LYP/STO-3G methods are reduced from 4.45 and 10.53 kcal·mol(-1) to 0.15 and 0.18 kcal·mol(-1), respectively. The improved results for the minimal basis set STO-3G reach the same accuracy as those of 6-31G(d), and thus B3LYP calculation with the minimal basis set is recommended to be used for minimizing the computational cost and to expand the applications to large molecular systems. Further extrapolation tests are performed with six molecules (two containing Si-NO bonds and two containing fluorine), and the accuracy of the tests was within 1 kcal·mol(-1). This study shows that DFT-SOFM-RBFNN is an efficient and highly accurate method for Y-NO homolysis BDE. The method may be used as a tool to design new NO carrier molecules.

  19. Wafer-level fabrication of GaN-based vertical light-emitting diodes using a multi-functional bonding material system

    International Nuclear Information System (INIS)

    Lee, Sang Youl; Choi, Kwang Ki; Jeong, Hwan-Hee; Choi, Hee Seok; Oh, Tchang-Hun; Song, June O; Seong, Tae-Yeon

    2009-01-01

    We first report on the fabrication of 2 inch wafer-level GaN-based vertical light-emitting diodes (LEDs) by using a multi-functional bonding material system, which is composed of a thick Cu diffusion barrier and a bonding layer. The bonding material system superbly absorbs laser-induced stress and also effectively serves as a barrier to the indiffusion of Sn to the active region. Fully packaged vertical LEDs fabricated with indium tin oxide (ITO)/AgCu contact and the bonding material system give an operating voltage of 3.35 V at 350 mA. After over 1800 h, the operating voltages remain stable, and the reverse currents are in the range 3–8 × 10 −7 A at −5 V. (rapid communication)

  20. Energy decomposition analysis of intermolecular interactions using a block-localized wave function approach

    Science.gov (United States)

    Mo, Yirong; Gao, Jiali; Peyerimhoff, Sigrid D.

    2000-04-01

    An energy decomposition scheme based on the block-localized wave function (BLW) method is proposed. The key of this scheme is the definition and the full optimization of the diabatic state wave function, where the charge transfer among interacting molecules is deactivated. The present energy decomposition (ED), BLW-ED, method is similar to the Morokuma decomposition scheme in definition of the energy terms, but differs in implementation and the computational algorithm. In addition, in the BLW-ED approach, the basis set superposition error is fully taken into account. The application of this scheme to the water dimer and the lithium cation-water clusters reveals that there is minimal charge transfer effect in hydrogen-bonded complexes. At the HF/aug-cc-PVTZ level, the electrostatic, polarization, and charge-transfer effects contribute 65%, 24%, and 11%, respectively, to the total bonding energy (-3.84 kcal/mol) in the water dimer. On the other hand, charge transfer effects are shown to be significant in Lewis acid-base complexes such as H3NSO3 and H3NBH3. In this work, the effect of basis sets used on the energy decomposition analysis is addressed and the results manifest that the present energy decomposition scheme is stable with a modest size of basis functions.

  1. Benchmarking Density Functional Theory Approaches for the Description of Symmetry-Breaking in Long Polymethine Dyes

    KAUST Repository

    Gieseking, Rebecca L.

    2016-04-25

    Long polymethines are well-known experimentally to symmetry-break, which dramatically modifies their linear and nonlinear optical properties. Computational modeling could be very useful to provide insight into the symmetry-breaking process, which is not readily available experimentally; however, accurately predicting the crossover point from symmetric to symmetry-broken structures has proven challenging. Here, we benchmark the accuracy of several DFT approaches relative to CCSD(T) geometries. In particular, we compare analogous hybrid and long-range corrected (LRC) functionals to clearly show the influence of the functional exchange term. Although both hybrid and LRC functionals can be tuned to reproduce the CCSD(T) geometries, the LRC functionals are better performing at reproducing the geometry evolution with chain length and provide a finite upper limit for the gas-phase crossover point; these methods also provide good agreement with the experimental crossover points for more complex polymethines in polar solvents. Using an approach based on LRC functionals, a reduction in the crossover length is found with increasing medium dielectric constant, which is related to localization of the excess charge on the end groups. Symmetry-breaking is associated with the appearance of an imaginary frequency of b2 symmetry involving a large change in the degree of bond-length alternation. Examination of the IR spectra show that short, isolated streptocyanines have a mode at ~1200 cm-1 involving a large change in bond-length alternation; as the polymethine length or the medium dielectric increases, the frequency of this mode decreases before becoming imaginary at the crossover point.

  2. EOMCC over excited state Hartree-Fock solutions (ESHF-EOMCC: An efficient approach for the entire ground state potential energy curves of higher-order bonds

    Directory of Open Access Journals (Sweden)

    Y. Sajeev

    2015-08-01

    Full Text Available The equation-of-motion coupled cluster (EOMCC method based on the excited state Hartree-Fock (ESHF solutions is shown to be appropriate for computing the entire ground state potential energy curves of strongly correlated higher-order bonds. The new approach is best illustrated for the homolytic dissociation of higher-order bonds in molecules. The required multireference character of the true ground state wavefunction is introduced through the linear excitation operator of the EOMCC method. Even at the singles and doubles level of cluster excitation truncation, the nonparallelity error of the ground state potential energy curve from the ESHF based EOMCC method is small.

  3. N-Oxide-N-oxide interactions and Cl...Cl halogen bonds in pentachloropyridine N-oxide: the many-body approach to interactions in the crystal state.

    Science.gov (United States)

    Wzgarda-Raj, Kinga; Rybarczyk-Pirek, Agnieszka J; Wojtulewski, Sławomir; Palusiak, Marcin

    2018-02-01

    Pentachloropyridine N-oxide, C 5 Cl 5 NO, crystallizes in the monoclinic space group P2 1 /c. In the crystal structure, molecules are linked by C-Cl...Cl halogen bonds into infinite ribbons extending along the crystallographic [100] direction. These molecular aggregates are further stabilized by very short intermolecular N-oxide-N-oxide interactions into herringbone motifs. Computations based on quantum chemistry methods allowed for a more detailed description of the N-oxide-N-oxide interactions and Cl...Cl halogen bonds. For this purpose, Hirshfeld surface analysis and the many-body approach to interaction energy were applied.

  4. Adhesive bond of veneering composites on various metal surfaces using silicoating, titanium-coating or functional monomers.

    Science.gov (United States)

    Behr, Michael; Rosentritt, Martin; Gröger, Gerhard; Handel, Gerhard

    2003-01-01

    This study compared the shear bond strength (SBS) between veneering composites and titanium (grade 1), a cobalt-chromium-alloy and a high precious-alloy, which were pretreated using silicoating systems, functional monomers or an experimental titanium-dioxide coating system. The specimens were sized to rectangular plates of 20 x10 x 2mm(3) (l,w,h) and a composite cylinder (height of 4mm, diameter 5mm) was axially polymerized to the middle of the plates. After aging (24h or 150 d storage in distilled water at 37 degrees C, or thermal-cycling: 6000 x 5 degrees /55 degrees C) the SBS was determined. Independent of the type of metal and the conditioning/coating techniques the lowest SBSs were found after thermal-cycling. Titanium. The SBS of the silica coating systems and the functional monomers did not differ statistically on titanium. However, the titanium-dioxide coating method had significantly higher values than the other methods. Cobalt-chromium. The highest mean values were observed with the titanium-dioxide coating system and the phosphate acid ester. Precious alloy. No statistical significant different SBS was found for the silicoating and the titanium-dioxide coating methods, while the functional monomers were statistically significant (lower) different to both systems. Generally, the titanium-dioxide coating system achieved the highest SBS under different aging conditions and on all three different metal-surfaces.

  5. Defining mental disorder. Exploring the 'natural function' approach

    Directory of Open Access Journals (Sweden)

    Varga Somogy

    2011-01-01

    Full Text Available Abstract Due to several socio-political factors, to many psychiatrists only a strictly objective definition of mental disorder, free of value components, seems really acceptable. In this paper, I will explore a variant of such an objectivist approach to defining metal disorder, natural function objectivism. Proponents of this approach make recourse to the notion of natural function in order to reach a value-free definition of mental disorder. The exploration of Christopher Boorse's 'biostatistical' account of natural function (1 will be followed an investigation of the 'hybrid naturalism' approach to natural functions by Jerome Wakefield (2. In the third part, I will explore two proposals that call into question the whole attempt to define mental disorder (3. I will conclude that while 'natural function objectivism' accounts fail to provide the backdrop for a reliable definition of mental disorder, there is no compelling reason to conclude that a definition cannot be achieved.

  6. Defining mental disorder. Exploring the 'natural function' approach.

    Science.gov (United States)

    Varga, Somogy

    2011-01-21

    Due to several socio-political factors, to many psychiatrists only a strictly objective definition of mental disorder, free of value components, seems really acceptable. In this paper, I will explore a variant of such an objectivist approach to defining metal disorder, natural function objectivism. Proponents of this approach make recourse to the notion of natural function in order to reach a value-free definition of mental disorder. The exploration of Christopher Boorse's 'biostatistical' account of natural function (1) will be followed an investigation of the 'hybrid naturalism' approach to natural functions by Jerome Wakefield (2). In the third part, I will explore two proposals that call into question the whole attempt to define mental disorder (3). I will conclude that while 'natural function objectivism' accounts fail to provide the backdrop for a reliable definition of mental disorder, there is no compelling reason to conclude that a definition cannot be achieved.

  7. Adhesive interfacial characteristics and the related bonding performance of four self-etching adhesives with different functional monomers applied to dentin.

    Science.gov (United States)

    Wang, Ruirui; Shi, Yilin; Li, Tingting; Pan, Yueping; Cui, Yu; Xia, Wenwei

    2017-07-01

    To examine the interfacial chemical and morphological characteristics of four self-etching adhesives bonded to dentin with different functional monomers. Further, to evaluate the effects of this interaction between functional monomers and dentin on short-term in vitro bonding performance of the four adhesives. Clearfil SE Bond (CSE) and Scotchbond Universal (SU) containing 10-methacryloxydecyl dihydrogen phosphate (10-MDP), Optibond XTR (OX) containing glycero-phosphate dimethacrylate (GPDM), and Adper Easy One (AEO) containing 6-methacryloyloxyhexyl dihydrogen phosphate (6-MHP) were applied to the dentin surface according to the instructions supplied with each. Interaction between the functional monomers and dentin was characterized using thin-film X-ray diffraction (TF-XRD) and scanning electron microscopy (SEM). The hydrophilicity of each acidic monomer was also assessed by chemical structure drawing software. Micro-tensile bond strength (μTBS) and nanoleakage were used to evaluate the bonding effectiveness of the adhesives, either immediately or after thermo-cycling (5°C-55°C) for 5000 cycles. TF-XRD showed that both CSE and SU exhibited 10-MDP-Ca nano-layering at the adhesive interface, but with different intensity when reacted with dentin. OX, that contains GPDM, demineralized the dentin surface more severely, forming long resin tags into the dentinal tubules, and gained the highest μTBS at the immediate time-point. Thermo-cycling adversely affected the μTBS and nanoleakage of AEO and OX, but had no significant influence on CSE and SU which contain 10-MDP. Self-etching adhesives containing different structures/concentrations of functional monomers produced adhesive interfaces with obviously different chemical and morphological characteristics, which may have a direct impact on bonding effectiveness. Our findings support the concept that the stable chemical bonding produced by 10-MDP to the Ca of hydroxyapatite is advantageous for durability of adhesive

  8. Study of chemical bonding in the interhalogen complexes based on density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Poleshchuk, O. Kh., E-mail: poleshch@tspu.edu.ru [National Research Tomsk Polytechnic University (Russian Federation); Fateev, A. V.; Yarkova, A. G. [Tomsk State Pedagogical University (Russian Federation); Ermakhanov, M. N.; Saidakhmetov, P. A. [M. Auezov South Kazakhstan State University (Kazakhstan)

    2016-12-15

    The density functional theory analysis was used for a number XYL complexes (XY is a dihalogen molecule and L is a Lewis base), formed between molecules I{sub 2}, ICl, IBr and pyridine. The calculated geometrical parameters, IR spectra and nuclear quadrupole interaction constants of iodine are consistent with the data of microwave spectroscopy and nuclear quadrupole resonance. The good correlation between the experimental and calculated binding energies of the inner electrons of iodine, chlorine and nitrogen atoms were found with the calculation using both Gaussian and Slater functions. The comparison of experimental and calculated changes in the electron density on the atoms upon complex formation suggested the choice of scheme for calculating the effective charge on the atoms, which allow us to interpret the experimental spectra. It is shown that the use of both calculated schemes allows us to predict the enthalpy of complex formation in close agreement with the experimental values. The energy analysis shows that in the complexes the electrostatic binding energy dominates that of covalent binding.

  9. A Functional Approach to the Choice between Descriptive ...

    African Journals Online (AJOL)

    Different types of prescription, description and proscription are discussed with specific reference to their potential use in dictionaries with text reception and text production as functions. Preferred approaches for the different functions are indicated. It is shown how an optimal use of a prescriptive, descriptive or proscriptive ...

  10. The roles of 4f- and 5f-orbitals in bonding: a magnetochemical, crystal field, density functional theory, and multi-reference wavefunction study.

    Science.gov (United States)

    Lukens, W W; Speldrich, M; Yang, P; Duignan, T J; Autschbach, J; Kögerler, P

    2016-07-28

    The electronic structures of 4f(3)/5f(3) Cp''3M and Cp''3M·alkylisocyanide complexes, where Cp'' is 1,3-bis-(trimethylsilyl)cyclopentadienyl, are explored with a focus on the splitting of the f-orbitals, which provides information about the strengths of the metal-ligand interactions. While the f-orbital splitting in many lanthanide complexes has been reported in detail, experimental determination of the f-orbital splitting in actinide complexes remains rare in systems other than halide and oxide compounds, since the experimental approach, crystal field analysis, is generally significantly more difficult for actinide complexes than for lanthanide complexes. In this study, a set of analogous neodymium(iii) and uranium(iii) tris-cyclopentadienyl complexes and their isocyanide adducts was characterized by electron paramagnetic resonance (EPR) spectroscopy and magnetic susceptibility. The crystal field model was parameterized by combined fitting of EPR and susceptibility data, yielding an accurate description of f-orbital splitting. The isocyanide derivatives were also studied using density functional theory, resulting in f-orbital splitting that is consistent with crystal field fitting, and by multi-reference wavefunction calculations that support the electronic structure analysis derived from the crystal-field calculations. The results highlight that the 5f-orbitals, but not the 4f-orbitals, are significantly involved in bonding to the isocyanide ligands. The main interaction between isocyanide ligand and the metal center is a σ-bond, with additional 5f to π* donation for the uranium complexes. While interaction with the isocyanide π*-orbitals lowers the energies of the 5fxz(2) and 5fyz(2)-orbitals, spin-orbit coupling greatly reduces the population of 5fxz(2) and 5fyz(2) in the ground state.

  11. Peculiar motions of galaxy clusters: correlation function approach

    Science.gov (United States)

    Iqbal, Naseer; Masood, Tabasum; Hamid, Mubashir; Ahmad, Naveel; Maqbool, Bari

    2014-10-01

    The correlation function theory on the basis of prescribed boundary conditions provides a deeper understanding in studying the dynamical parameters of galaxy clusters. The approach approximates that the moderate dense systems discussed by a two point correlation function is helpful for describing the dynamical nature of galaxy clusters. The projected theory of two point correlation function for point mass and extended mass structures can be used an alternative tool in measuring the average peculiar motion and temperature profile of galaxy clusters.

  12. Method of Moments of Coupled-Cluster Equations: Externally Corrected Approaches Employing Configuration Interaction Wave Functions

    Directory of Open Access Journals (Sweden)

    Ian S.O. Pimienta

    2002-05-01

    Full Text Available Abstract: A new approach to the many-electron correlation problem, termed the method of moments of coupled-cluster equations (MMCC, is further developed and tested. The main idea of the MMCC theory is that of the noniterative energy corrections which, when added to the energies obtained in the standard coupled-cluster calculations, recover the exact (full configuration interaction energy. The MMCC approximations require that a guess is provided for the electronic wave function of interest. The idea of using simple estimates of the wave function, provided by the inexpensive configuration interaction (CI methods employing small sets of active orbitals to define higher–than–double excitations, is tested in this work. The CI-corrected MMCC methods are used to study the single bond breaking in HF and the simultaneous breaking of both O–H bonds in H2O.

  13. Density functional theory based-study of 5-fluorouracil adsorption on β-cristobalite (1 1 1) hydroxylated surface: The importance of H-bonding interactions

    Energy Technology Data Exchange (ETDEWEB)

    Simonetti, S., E-mail: ssimonet@uns.edu.ar [Universidad Nacional del Sur (UNS)—Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Bahía Blanca (Argentina); Universidad Tecnológica Nacional (UTN), Bahía Blanca (Argentina); Compañy, A. Díaz [Comisión de Investigaciones Científicas (CIC), Buenos Aires (Argentina); Pronsato, E.; Juan, A.; Brizuela, G. [Universidad Nacional del Sur (UNS)—Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Bahía Blanca (Argentina); Lam, A. [Instituto de Ciencia y Tecnología de Materiales (IMRE), Universidad de La Habana (Cuba)

    2015-12-30

    Graphical abstract: - Highlights: • Favorable energies results in optimum four adsorption geometries. • Silanols are partially weakening and establish H-bonds with polar groups of 5-FU drug. • Dispersion forces approach the 5-FU molecule toward the surface. • Electron exchange is presented after adsorption. • H-bonds stabilize the molecule playing significant role in the adsorption mechanism. - Abstract: Silica-based mesoporous materials have been recently proposed as an efficient support for the controlled release of a popular anticancer drug, 5-fluorouracil (5-FU). Although the relevance of this topic, the atomistic details about the specific surface-drug interactions and the energy of adsorption are almost unknown. In this work, theoretical calculations using the Vienna Ab-initio Simulation Package (VASP) applying Grimme's—D2 correction were performed to elucidate the drug–silica interactions and the host properties that control 5-FU drug adsorption on β-cristobalite (1 1 1) hydroxylated surface. This study shows that hydrogen bonding, electron exchange, and dispersion forces are mainly involved to perform the 5-FU adsorption onto silica. This phenomenon, revealed by favorable energies, results in optimum four adsorption geometries that can be adopted for 5-FU on the hydroxylated silica surface. Silanols are weakening in response to the molecule approach and establish H-bonds with polar groups of 5-FU drug. The final geometry of 5-FU adopted on hydroxylated silica surface is the results of H-bonding interactions which stabilize and fix the molecule to the surface and dispersion forces which approach it toward silica (1 1 1) plane. The level of hydroxylation of the SiO{sub 2} (1 1 1) surface is reflected by the elevated number of hydrogen bonds that play a significant role in the adsorption mechanisms.

  14. Self-Reported Emotional and Behavioral Problems, Family Functioning and Parental Bonding among Psychiatric Outpatient Adolescent Offspring of Croatian Male Veterans with Partial PTSD

    Science.gov (United States)

    Sarajlic Vukovic, Iris; Boricevic Maršanic, Vlatka; Aukst Margetic, Branka; Paradžik, Ljubica; Vidovic, Domagoj; Buljan Flander, Gordana

    2015-01-01

    Background: Posttraumatic stress disorder (PTSD) in male veterans has been linked with impaired family relationships and psychopathology in their children. Less is known about symptoms in children of veterans with partial PTSD. Objective: To compare mental health problems, family functioning and parent-child bonding among adolescent offspring of…

  15. A review of function modeling: Approaches and applications

    OpenAIRE

    Erden, M.S.; Komoto, H.; Van Beek, T.J.; D'Amelio, V.; Echavarria, E.; Tomiyama, T.

    2008-01-01

    This work is aimed at establishing a common frame and understanding of function modeling (FM) for our ongoing research activities. A comparative review of the literature is performed to grasp the various FM approaches with their commonalities and differences. The relations of FM with the research fields of artificial intelligence, design theory, and maintenance are discussed. In this discussion the goals are to highlight the features of various classical approaches in relation to FM, to delin...

  16. Iron-catalyzed oxidative sp3carbon-hydrogen bond functionalization of 3,4-dihydro-1,4-benzoxazin-2-ones.

    Science.gov (United States)

    Huo, Congde; Dong, Jie; Su, Yingpeng; Tang, Jing; Chen, Fengjuan

    2016-11-08

    A novel and efficient iron-catalyzed sp 3 carbon-hydrogen bond functionalization of benzoxazinone derivatives has been developed. For the first time, benzoxazin-2-ones were used as substrates in an oxidative dehydrogenative coupling reaction. The experiments were performed under mild reaction conditions to construct alkyl-aryl C(sp 3 )-C(sp 2 ) bonds. The application of this method to the gram-scale synthesis of natural product cephalandole A has been accomplished in a 3-step sequence. A plausible one electron oxidation involved mechanism is proposed.

  17. Phytochemical, spectroscopic and density functional theory study of Diospyrin, and non-bonding interactions of Diospyrin with atmospheric gases

    Science.gov (United States)

    Fazl-i-Sattar; Ullah, Zakir; Ata-ur-Rahman; Rauf, Abdur; Tariq, Muhammad; Tahir, Asif Ali; Ayub, Khurshid; Ullah, Habib

    2015-04-01

    Density functional theory (DFT) and phytochemical study of a natural product, Diospyrin (DO) have been carried out. A suitable level of theory was developed, based on correlating the experimental and theoretical data. Hybrid DFT method at B3LYP/6-31G (d,p) level of theory is employed for obtaining the electronic, spectroscopic, inter-molecular interaction and thermodynamic properties of DO. The exact structure of DO is confirmed from the nice validation of the theory and experiment. Non-covalent interactions of DO with different atmospheric gases such as NH3, CO2, CO, and H2O were studied to find out its electroactive nature. The experimental and predicted geometrical parameters, IR and UV-vis spectra (B3LYP/6-31+G (d,p) level of theory) show excellent correlation. Inter-molecular non-bonding interaction of DO with atmospheric gases is investigated through geometrical parameters, electronic properties, charge analysis, and thermodynamic parameters. Electronic properties include, ionization potential (I.P.), electron affinities (E.A.), electrostatic potential (ESP), density of states (DOS), HOMO, LUMO, and band gap. All these characterizations have corroborated each other and confirmed the presence of non-covalent nature in DO with the mentioned gases.

  18. Phytochemical, spectroscopic and density functional theory study of Diospyrin, and non-bonding interactions of Diospyrin with atmospheric gases.

    Science.gov (United States)

    Fazl-i-Sattar; Ullah, Zakir; Ata-ur-Rahman; Rauf, Abdur; Tariq, Muhammad; Tahir, Asif Ali; Ayub, Khurshid; Ullah, Habib

    2015-04-15

    Density functional theory (DFT) and phytochemical study of a natural product, Diospyrin (DO) have been carried out. A suitable level of theory was developed, based on correlating the experimental and theoretical data. Hybrid DFT method at B3LYP/6-31G (d,p) level of theory is employed for obtaining the electronic, spectroscopic, inter-molecular interaction and thermodynamic properties of DO. The exact structure of DO is confirmed from the nice validation of the theory and experiment. Non-covalent interactions of DO with different atmospheric gases such as NH3, CO2, CO, and H2O were studied to find out its electroactive nature. The experimental and predicted geometrical parameters, IR and UV-vis spectra (B3LYP/6-31+G (d,p) level of theory) show excellent correlation. Inter-molecular non-bonding interaction of DO with atmospheric gases is investigated through geometrical parameters, electronic properties, charge analysis, and thermodynamic parameters. Electronic properties include, ionization potential (I.P.), electron affinities (E.A.), electrostatic potential (ESP), density of states (DOS), HOMO, LUMO, and band gap. All these characterizations have corroborated each other and confirmed the presence of non-covalent nature in DO with the mentioned gases. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Estimating variability in functional images using a synthetic resampling approach

    International Nuclear Information System (INIS)

    Maitra, R.; O'Sullivan, F.

    1996-01-01

    Functional imaging of biologic parameters like in vivo tissue metabolism is made possible by Positron Emission Tomography (PET). Many techniques, such as mixture analysis, have been suggested for extracting such images from dynamic sequences of reconstructed PET scans. Methods for assessing the variability in these functional images are of scientific interest. The nonlinearity of the methods used in the mixture analysis approach makes analytic formulae for estimating variability intractable. The usual resampling approach is infeasible because of the prohibitive computational effort in simulating a number of sinogram. datasets, applying image reconstruction, and generating parametric images for each replication. Here we introduce an approach that approximates the distribution of the reconstructed PET images by a Gaussian random field and generates synthetic realizations in the imaging domain. This eliminates the reconstruction steps in generating each simulated functional image and is therefore practical. Results of experiments done to evaluate the approach on a model one-dimensional problem are very encouraging. Post-processing of the estimated variances is seen to improve the accuracy of the estimation method. Mixture analysis is used to estimate functional images; however, the suggested approach is general enough to extend to other parametric imaging methods

  20. Interprofessional approach for teaching functional knee joint anatomy.

    Science.gov (United States)

    Meyer, Jakob J; Obmann, Markus M; Gießler, Marianne; Schuldis, Dominik; Brückner, Ann-Kathrin; Strohm, Peter C; Sandeck, Florian; Spittau, Björn

    2017-03-01

    Profound knowledge in functional and clinical anatomy is a prerequisite for efficient diagnosis in medical practice. However, anatomy teaching does not always consider functional and clinical aspects. Here we introduce a new interprofessional approach to effectively teach the anatomy of the knee joint. The presented teaching approach involves anatomists, orthopaedists and physical therapists to teach anatomy of the knee joint in small groups under functional and clinical aspects. The knee joint courses were implemented during early stages of the medical curriculum and medical students were grouped with students of physical therapy to sensitize students to the importance of interprofessional work. Evaluation results clearly demonstrate that medical students and physical therapy students appreciated this teaching approach. First evaluations of following curricular anatomy exams suggest a benefit of course participants in knee-related multiple choice questions. Together, the interprofessional approach presented here proves to be a suitable approach to teach functional and clinical anatomy of the knee joint and further trains interprofessional work between prospective physicians and physical therapists as a basis for successful healthcare management. Copyright © 2016 The Authors. Published by Elsevier GmbH.. All rights reserved.

  1. A Green's function approach to giant-dipole systems

    Science.gov (United States)

    Stielow, Thomas; Scheel, Stefan; Kurz, Markus

    2018-01-01

    In this work we perform a Green’s function analysis of giant-dipole systems. First, we derive the Green’s functions of different magnetically field-dressed systems, in particular of electronically highly excited atomic species in crossed electric and magnetic fields—so-called giant-dipole states. We determine the dynamical polarizability of atomic giant-dipole states as well as the adiabatic potential energy surfaces of giant-dipole molecules in the framework of the Green’s function approach. Furthermore, we perform an comparative analysis of the latter to an exact diagonalization scheme and show the general divergence behavior of the widely applied Fermi-pseudopotential approach. Finally, we derive the giant-dipole’s regularized Green’s function representation.

  2. Estimating Money Demand Function in Cambodia: ARDL Approach

    OpenAIRE

    Samreth, Sovannroeun

    2008-01-01

    This paper empirically estimates the money demand function in Cambodia. We adopt the money demand model that includes exchange rate. For the analysis, Autoregressive Distributed Lag (ARDL) approach to cointegration is employed. Our results indicate that there is cointegration among variables in money demand function. CUSUM and CUSUMSQ tests roughly support the stability of estimated model. However, in the long-run, even the sign of estimated coefficient of exchange rate support the currency s...

  3. Pediatrician's knowledge on the approach of functional constipation

    OpenAIRE

    Vieira, Mario C.; Negrelle, Isadora Carolina Krueger; Webber, Karla Ulaf; Gosdal, Marjorie; Truppel, Sabine Krüger; Kusma, Solena Ziemer

    2016-01-01

    Abstract Objective: To evaluate the pediatrician's knowledge regarding the diagnostic and therapeutic approach of childhood functional constipation. Methods: A descriptive cross-sectional study was performed with the application of a self-administered questionnaire concerning a hypothetical clinical case of childhood functional constipation with fecal incontinence to physicians (n=297) randomly interviewed at the 36th Brazilian Congress of Pediatrics in 2013. Results: The majority of the p...

  4. A Novel Synchronization-Based Approach for Functional Connectivity Analysis

    Directory of Open Access Journals (Sweden)

    Angela Lombardi

    2017-01-01

    Full Text Available Complex network analysis has become a gold standard to investigate functional connectivity in the human brain. Popular approaches for quantifying functional coupling between fMRI time series are linear zero-lag correlation methods; however, they might reveal only partial aspects of the functional links between brain areas. In this work, we propose a novel approach for assessing functional coupling between fMRI time series and constructing functional brain networks. A phase space framework is used to map couples of signals exploiting their cross recurrence plots (CRPs to compare the trajectories of the interacting systems. A synchronization metric is extracted from the CRP to assess the coupling behavior of the time series. Since the functional communities of a healthy population are expected to be highly consistent for the same task, we defined functional networks of task-related fMRI data of a cohort of healthy subjects and applied a modularity algorithm in order to determine the community structures of the networks. The within-group similarity of communities is evaluated to verify whether such new metric is robust enough against noise. The synchronization metric is also compared with Pearson’s correlation coefficient and the detected communities seem to better reflect the functional brain organization during the specific task.

  5. Structural, bonding, and electronic properties of the hexagonal ferroelectric and paraelectric phases of LuMnO{sub 3} compound: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Sousa, A. M.; Coutinho, W. S.; Lima, A. F.; Lalic, M. V., E-mail: mlalicbr@gmail.com [Physics Department, Federal University of Sergipe, São Cristóvão 49100-000 (Brazil)

    2015-02-21

    We have investigated the structural, bonding, and electronic properties of both ferroelectric (FE) and paraelectric (PE) phases of the hexagonal LuMnO{sub 3} compound using calculations based on density functional theory. The structural properties have been determined by employing the generalized gradient approximation with Perdew-Burke-Ernzerhof and Wu-Cohen parameterization. The bonding and electronic properties have been treated by recently developed modified Becke-Johnson exchange potential, which succeeded to open a band gap for both PE and FE phases, in agreement with experimental predictions. The Bader’s topological analysis of electronic density showed that the character of the Lu–O axial bonds changes when the crystal exhibits the PE → FE structural transition. This fact is in agreement with experimental findings. The covalent character of the Lu–O bond significantly increases due to orbital hybridization between the Lu 5d{sub z}{sup 2} and O 2p{sub z}-states. This bonding mechanism causes the ferroelectricity in the hexagonal LuMnO{sub 3} compound.

  6. Self-reported emotional and behavioral symptoms, parent-adolescent bonding and family functioning in clinically referred adolescent offspring of Croatian PTSD war veterans.

    Science.gov (United States)

    Boričević Maršanić, Vlatka; Aukst Margetić, Branka; Jukić, Vlado; Matko, Vlasta; Grgić, Vesna

    2014-05-01

    The presence of posttraumatic stress disorder (PTSD) in male war veterans has been linked with family dysfunction and psychopathology in their children [1, 2]. This study aimed to evaluate self-reported emotional and behavioral symptoms, parent-adolescent bonding and family functioning in clinically referred adolescent offspring of Croatian PTSD war veterans and determine the degree that parent-child bonding and family functioning contributed to adolescent behavior problems. Internalizing and externalizing behavior problems, parent-child bonding and family functioning were assessed in a sample of clinically referred Croatian PTSD veterans adolescent offspring (N = 122) and non-PTSD veteran adolescent offspring (N = 122) matched for age, sex, educational level, family income, parental employment status, ethnicity, and residential area. Youth Self-Report, Parental Bonding Instrument, Family Assessment Device were used. Adolescent offspring of PTSD veterans reported having significantly more internalizing and externalizing problems than non-PTSD veteran offspring, and also more difficulties in their family functioning, lower levels of maternal and paternal care, and more impaired mother-child and father-child bonding than control subjects. Internalizing symptoms were associated with family dysfunction, while externalizing symptoms were associated with paternal overcontrol/overprotection, and low maternal and paternal care. In conclusion, the increase in internalizing and externalizing symptoms as well as family and parental dysfunction among clinically referred adolescent offspring of PTSD veterans compared to their non-PTSD veteran counterparts indicates a need for early detection and interventions targeting both adolescent psychopathology and family relationships.

  7. The Feynman-Vernon Influence Functional Approach in QED

    International Nuclear Information System (INIS)

    Biryukov, Alexander; Shleenkov, Mark

    2016-01-01

    In the path integral approach we describe evolution of interacting electromagnetic and fermionic fields by the use of density matrix formalism. The equation for density matrix and transitions probability for fermionic field is obtained as average of electromagnetic field influence functional. We obtain a formula for electromagnetic field influence functional calculating for its various initial and final state. We derive electromagnetic field influence functional when its initial and final states are vacuum. We present Lagrangian for relativistic fermionic field under influence of electromagnetic field vacuum

  8. Coupled cluster approach to the single-particle Green's function

    International Nuclear Information System (INIS)

    Nooijen, M.; Snijders, J.G.

    1992-01-01

    Diagrammatic and coupled cluster techniques are used to develop an approach to the single-particle Green's function G which concentrates on G directly rather than first approximating the irreducible self-energy and then solving Dyson's equation. As a consequence the ionization and attachment parts of the Green's function satisfy completely decoupled sets of equations. The proposed coupled cluster Green's function method (CCGF) is intimately connected to both coupled cluster linear response theory (CCLRT) and the normal coupled cluster method (NCCM). These relations are discussed in detail

  9. Chemisorption bonding and catalysis

    International Nuclear Information System (INIS)

    Danese, J.B.; Schrieffer, J.R.

    1976-01-01

    The general features of the LCAO--MO, Green's function, and multiple-scattering chi α methods and their applications to surfaces and surface-related problems are discussed. Emphasis is placed on the localization of bonding in surface complexes

  10. A review of function modeling : Approaches and applications

    NARCIS (Netherlands)

    Erden, M.S.; Komoto, H.; Van Beek, T.J.; D'Amelio, V.; Echavarria, E.; Tomiyama, T.

    2008-01-01

    This work is aimed at establishing a common frame and understanding of function modeling (FM) for our ongoing research activities. A comparative review of the literature is performed to grasp the various FM approaches with their commonalities and differences. The relations of FM with the research

  11. Questionnaire of Executive Function for Dancers: An Ecological Approach

    Science.gov (United States)

    Wong, Alina; Rodriguez, Mabel; Quevedo, Liliana; de Cossio, Lourdes Fernandez; Borges, Ariel; Reyes, Alicia; Corral, Roberto; Blanco, Florentino; Alvarez, Miguel

    2012-01-01

    There is a current debate about the ecological validity of executive function (EF) tests. Consistent with the verisimilitude approach, this research proposes the Ballet Executive Scale (BES), a self-rating questionnaire that assimilates idiosyncratic executive behaviors of classical dance community. The BES was administrated to 149 adolescents,…

  12. A solution-state NMR approach to elucidating pMDI-wood bonding mechanisms in loblolly pine

    Science.gov (United States)

    Daniel Joseph Yelle

    2009-01-01

    Solution-state NMR spectroscopy is a powerful tool for unambiguously determining the existence or absence of covalent chemical bonds between wood components and adhesives. Finely ground wood cell wall material dissolves in a solvent system containing DMSO-d6 and NMI-d6, keeping wood component polymers intact and in a near-...

  13. New Raman method for aqueous solutions: xi-function dispersion evidence for strong F(-)-water H-bonds in aqueous CsF and KF solutions.

    Science.gov (United States)

    Walrafen, George E

    2005-08-15

    The Raman xi-function dispersion method recently elucidated for the strong H-bond breaker, ClO4-, in water [G. E. Walrafen, J. Chem. Phys. 122, 094510 (2005)] is extended to the strongly H-bond forming ion, F-. Measuring the xi function is analogous to measuring DeltaG from the thermodynamic activity of the water, aH2O, as the stoichiometric mol fraction of the water in the solution decreases due to addition of an electrolyte or nonelectrolyte. xi is the derivative of the OH-stretching part of the Gibbs free energy with respect to the water mol fraction; xiomega identical with-RT[ partial differential ln(Iomega/IREF) partial differentialX2](T,P). I is the Raman intensity at omega (omega=Raman shift in cm-1); IREF, that at an arbitrary reference omega; and, X2 is the water mol fraction (X1=CsF or KF mol fraction). ln(Iomega/IREF) was found to be linear in X2 for the complete range of OH-stretching omega's, with correlation coefficients as large as 0.999 96. Linearity of ln(Iomega/IREF) versus X2 is an experimental fact for all omega's throughout the spontaneous Raman OH-stretching contour; this fact cannot be negated by relative contributions of ultrafast/fast, homogeneous/inhomogeneous processes which may underlie this linearity. Linearity in ln(Iomega/IREF) versus 1T, or in ln(Iomega/IREF) versus P, was also observed for the Raman H-bond energy DeltaE and pair volume DeltaV dispersions, respectively. A low-frequency maximum (MAX) and a high-frequency minimum (MIN) were observed in the xi function dispersion curve. Deltaxi=xiMIN-xiMAX values of -7000+/-800-cal/mol H2O for CsF, and the experimentally equal Deltaxi=-6400+/-1000-cal/mol H2O for KF, were obtained. These Deltaxi's are opposite in sign but have nearly the same absolute magnitude as the Deltaxi value for NaClO4 in water; Deltaxi=+8050+/-100-cal/mol H2O. A positive Deltaxi corresponds to a water-water H-bond breaker; a negative Deltaxi to a H-bond former; specifically, a F--water H-bond former, in the

  14. A reduced radial potential energy function for the halogen bond and the hydrogen bond in complexes B···XY and B···HX, where X and Y are halogen atoms.

    Science.gov (United States)

    Legon, Anthony C

    2014-06-28

    It is shown by considering 76 halogen- and hydrogen-bonded complexes BXY and BHX (where B is a Lewis base N2, CO, C2H2, C2H4, H2S, HCN, H2O, PH3 or NH3 and X, Y are F, Cl, Br or I) that the intermolecular stretching force constants kσ (determined from experimental centrifugal distortion constants via a simple model) and the intermolecular dissociation energies Dσ (calculated at the CCSD(T)(F12*)/cc-pVDZ-F12 level of theory) are related by Dσ = Cσkσ, where Cσ = 1.50(3) × 10(3) m(2) mol(-1). This suggests that one-dimensional functions implying direct proportionality of Dσ and kσ, (e.g. a Morse or Rydberg function) might serve as reduced radial potential energy functions for such complexes.

  15. Magnetic circular dichroism and density functional theory studies of electronic structure and bonding in cobalt(ii)-N-heterocyclic carbene complexes.

    Science.gov (United States)

    Iannuzzi, Theresa E; Gao, Yafei; Baker, Tessa M; Deng, Liang; Neidig, Michael L

    2017-10-10

    The combination of simple cobalt salts and N-heterocyclic carbene (NHC) ligands has been highly effective in C-H functionalization, hydroarylation and cross-coupling catalysis, though displaying a strong dependence on the identity of the NHC ligand. In addition, reactions effective with NHC ligands are often ineffective with phosphine ligands, further motivating the evaluation of the fundamental electronic structure and bonding differences in well-defined distorted tetrahedral Co(ii) complexes. Magnetic circular dichroism (MCD) studies indicate that Co(ii)-bisphosphines have larger ligand fields than Co(ii)-NHC complexes. Theoretical density functional theory (DFT) calculations were performed on an expanded set of L 2 CoCl 2 complexes (L 2 = NHC, bisphosphine and diamine) to study the electronic structure and relative ligation properties of NHCs compared to bisphosphine and diamine ligands. Mayer bond order and charge decomposition analyses indicate that NHC ligands are slightly stronger donor ligands than bisphosphines but also result in a weakening of Co-Cl bonds in a trans-like influence. From MCD and DFT studies, changing the NHC N-substituent has a larger effect on the ligand field of Co(ii)-NHC complexes than saturating the backbone. Overall, these studies provide detailed insight into the electronic structure and bonding effects in Co(ii) complexes with ligand types commonly explored in catalysis.

  16. Redox-Triggered Bonding-Induced Emission of Thiol-Functionalized Gold Nanoclusters for Luminescence Turn-On Detection of Molecular Oxygen.

    Science.gov (United States)

    Ao, Hang; Feng, Hui; Zhao, Mengting; Zhao, Meizhi; Chen, Jianrong; Qian, Zhaosheng

    2017-11-22

    Most optical sensors for molecular oxygen were developed based on the quenching effect of the luminescence of oxygen-sensitive probes; however, the signal turn-off mode of these probes is undesirable to quantify and visualize molecular oxygen. Herein, we report a novel luminescence turn-on detection strategy for molecular oxygen via the specific oxygen-triggered bonding-induced emission of thiol-functionalized gold nanoclusters. Thiol-functionalized gold nanoclusters were prepared by a facile one-step synthesis, and as-prepared gold nanoclusters possess significant aggregation-induced emission (AIE) property. It is the first time to discover the oxygen-triggered bonding-induced emission (BIE) behavior of gold nanoclusters, which results in disulfide-linked covalent bonding assemblies with intensely red luminescence. This specific redox-triggered BIE is capable of quantitatively detecting dissolved oxygen in aqueous solution in a light-up manner, and trace amount of dissolved oxygen at ppb level is achieved based on this detection method. A facile and convenient test strip for oxygen detection was also developed to monitor molecular oxygen in a gas matrix. Covalent bonding-induced emission is proven to be a more efficient way to attain high brightness of AIEgens than a physical aggregation-induced emission process, and provides a more convenient and desirable detection method for molecular oxygen than the previous sensors.

  17. Beta-1 integrin-mediated adhesion may be initiated by multiple incomplete bonds, thus accounting for the functional importance of receptor clustering.

    Science.gov (United States)

    Vitte, Joana; Benoliel, Anne-Marie; Eymeric, Philippe; Bongrand, Pierre; Pierres, Anne

    2004-06-01

    The regulation of cell integrin receptors involves modulation of membrane expression, shift between different affinity states, and topographical redistribution on the cell membrane. Here we attempted to assess quantitatively the functional importance of receptor clustering. We studied beta-1 integrin-mediated attachment of THP-1 cells to fibronectin-coated surfaces under low shear flow. Cells displayed multiple binding events with a half-life of the order of 1 s. The duration of binding events after the first second after arrest was quantitatively accounted for by a model assuming the existence of a short-time intermediate binding state with 3.6 s(-1) dissociation rate and 1.3 s(-1) transition frequency toward a more stable state. Cell binding to surfaces coated with lower fibronectin densities was concluded to be mediated by single molecular interactions, whereas multiple bonds were formed Cell treatment with microfilament inhibitors or a neutral antiintegrin antibody decreased bond number without changing aforementioned kinetic parameters whereas a function enhancing antibody increased the rate of bond formation and/or the lifetime of intermediate state. Receptor aggregation was induced by treating cells with neutral antiintegrin antibody and antiimmunoglobulin antibodies. A semiquantitative confocal microscopy study suggested that this treatment increased between 40% and 100% the average number of integrin receptors located in a volume of approximately 0.045 microm(3) surrounding each integrin. This aggregation induced up to 2.7-fold increase of the average number of bonds. Flow cytometric analysis of fluorescent ligand binding showed that THP-1 cells displayed low-affinity beta-1 integrins with a dissociation constant in the micromolar range. It is concluded that the initial step of cell adhesion was mediated by multiple incomplete bonds rather than a single equilibrium-state ligand receptor association. This interpretation accounts for the functional

  18. Anion-based approaches to tunable functionality in oxide heterostructures

    Science.gov (United States)

    May, Steven

    2014-03-01

    The ability to control the position and composition of the anion site is emerging as a promising route to tune properties in epitaxial perovskites. This talk will focus on recent and ongoing efforts aimed at developing anion-based approaches to tailor electronic and magnetic properties in oxide films. First, I will discuss how the position of the oxygen anions can be tailored to stabilize non-bulk-like bond angles and lengths, thereby altering electronic bandwidth. Recent work on La2/3Sr1/3MnO3 will be presented in which ultrathin films under the same strain state exhibit dramatically different electronic and magnetic properties when grown on substrates with different symmetries. In the second half of the talk, I will describe efforts focused on altering the composition of the anion site. In La1/3Sr2/3FeO3-δ films, a reversible change in oxygen content leads to dramatic changes in electrical, optical, and structural properties. Finally, the synthesis of oxyfluoride ferrite and nickelate perovskite films via topotactic reactions carried out following thin film deposition will be described. This work is supported by the Office of Naval Research (N00014-11-1-0664) and the U. S. Army Research Office (W911NF-12-1-0132).

  19. An evolutionary computation approach to examine functional brain plasticity

    Directory of Open Access Journals (Sweden)

    Arnab eRoy

    2016-04-01

    Full Text Available One common research goal in systems neurosciences is to understand how the functional relationship between a pair of regions of interest (ROIs evolves over time. Examining neural connectivity in this way is well-suited for the study of developmental processes, learning, and even in recovery or treatment designs in response to injury. For most fMRI based studies, the strength of the functional relationship between two ROIs is defined as the correlation between the average signal representing each region. The drawback to this approach is that much information is lost due to averaging heterogeneous voxels, and therefore, the functional relationship between a ROI-pair that evolve at a spatial scale much finer than the ROIs remain undetected. To address this shortcoming, we introduce a novel evolutionary computation (EC based voxel-level procedure to examine functional plasticity between an investigator defined ROI-pair by simultaneously using subject-specific BOLD-fMRI data collected from two sessions seperated by finite duration of time. This data-driven procedure detects a sub-region composed of spatially connected voxels from each ROI (a so-called sub-regional-pair such that the pair shows a significant gain/loss of functional relationship strength across the two time points. The procedure is recursive and iteratively finds all statistically significant sub-regional-pairs within the ROIs. Using this approach, we examine functional plasticity between the default mode network (DMN and the executive control network (ECN during recovery from traumatic brain injury (TBI; the study includes 14 TBI and 12 healthy control subjects. We demonstrate that the EC based procedure is able to detect functional plasticity where a traditional averaging based approach fails. The subject-specific plasticity estimates obtained using the EC-procedure are highly consistent across multiple runs. Group-level analyses using these plasticity estimates showed an increase in

  20. A Unified Approach to Functional Principal Component Analysis and Functional Multiple-Set Canonical Correlation.

    Science.gov (United States)

    Choi, Ji Yeh; Hwang, Heungsun; Yamamoto, Michio; Jung, Kwanghee; Woodward, Todd S

    2017-06-01

    Functional principal component analysis (FPCA) and functional multiple-set canonical correlation analysis (FMCCA) are data reduction techniques for functional data that are collected in the form of smooth curves or functions over a continuum such as time or space. In FPCA, low-dimensional components are extracted from a single functional dataset such that they explain the most variance of the dataset, whereas in FMCCA, low-dimensional components are obtained from each of multiple functional datasets in such a way that the associations among the components are maximized across the different sets. In this paper, we propose a unified approach to FPCA and FMCCA. The proposed approach subsumes both techniques as special cases. Furthermore, it permits a compromise between the techniques, such that components are obtained from each set of functional data to maximize their associations across different datasets, while accounting for the variance of the data well. We propose a single optimization criterion for the proposed approach, and develop an alternating regularized least squares algorithm to minimize the criterion in combination with basis function approximations to functions. We conduct a simulation study to investigate the performance of the proposed approach based on synthetic data. We also apply the approach for the analysis of multiple-subject functional magnetic resonance imaging data to obtain low-dimensional components of blood-oxygen level-dependent signal changes of the brain over time, which are highly correlated across the subjects as well as representative of the data. The extracted components are used to identify networks of neural activity that are commonly activated across the subjects while carrying out a working memory task.

  1. COMPUTATIONAL APPROACHES FOR RATIONAL DESIGN OF PROTEINS WITH NOVEL FUNCTIONALITIES

    Directory of Open Access Journals (Sweden)

    Manish Kumar Tiwari

    2012-09-01

    Full Text Available Proteins are the most multifaceted macromolecules in living systems and have various important functions, including structural, catalytic, sensory, and regulatory functions. Rational design of enzymes is a great challenge to our understanding of protein structure and physical chemistry and has numerous potential applications. Protein design algorithms have been applied to design or engineer proteins that fold, fold faster, catalyze, catalyze faster, signal, and adopt preferred conformational states. The field of de novo protein design, although only a few decades old, is beginning to produce exciting results. Developments in this field are already having a significant impact on biotechnology and chemical biology. The application of powerful computational methods for functional protein designing has recently succeeded at engineering target activities. Here, we review recently reported de novo functional proteins that were developed using various protein design approaches, including rational design, computational optimization, and selection from combinatorial libraries, highlighting recent advances and successes.

  2. Elements of a function analytic approach to probability.

    Energy Technology Data Exchange (ETDEWEB)

    Ghanem, Roger Georges (University of Southern California, Los Angeles, CA); Red-Horse, John Robert

    2008-02-01

    We first provide a detailed motivation for using probability theory as a mathematical context in which to analyze engineering and scientific systems that possess uncertainties. We then present introductory notes on the function analytic approach to probabilistic analysis, emphasizing the connections to various classical deterministic mathematical analysis elements. Lastly, we describe how to use the approach as a means to augment deterministic analysis methods in a particular Hilbert space context, and thus enable a rigorous framework for commingling deterministic and probabilistic analysis tools in an application setting.

  3. Modified precision lingual bonding technique: A step-wise approach with torque angulation device-bracket positioning device

    Directory of Open Access Journals (Sweden)

    Rosaline Tina Paul

    2017-01-01

    Full Text Available Objectives: Contemporary preadjusted edgewise appliance is all about the precision in bracket design, prescription and positioning in addition to the orthodontist's skill and training. However, achieving it is a bigger challenge as the anatomy of the lingual surface of a tooth is uneven, dissimilar, and moreover the tooth alignment on the lingual surface is variant. Thus, the need for an accurate method of bracket positioning with predetermined torque and angulation incorporated in the brackets according to the patients' need is of key importance. Materials and Methods: A TAD-BPD machine used to enhance the accuracy of bracket positioning and bioplast accurate tray transfer technique was used. Results: A step-wise procedures in bracket positioning and fabricating an indirect bonding tray for lingual orthodontics using the torque angulation device-bracket positioning device. Conclusions: This technique facilitated unhindered bonding even in severely crowded cases and easy rebonding during mid-treatment stages.

  4. Assessment of Cardiac Function--Basic Principles and Approaches.

    Science.gov (United States)

    Spinale, Francis G

    2015-09-20

    Increased access and ability to visualize the heart has provided a means to measure a myriad of cardiovascular parameters in real or near real time. However, without fundamental knowledge regarding the basis for cardiac contraction and how to evaluate cardiac function in terms of loading conditions and inotropic state, appropriate interpretation of these cardiovascular parameters can be difficult and can lead to misleading conclusions regarding the functional state of the cardiac muscle. Thus, in this series of Comprehensive Physiology, the basic properties of cardiac muscle function, the cardiac cycle, and determinants of pump function will be reviewed. These basic concepts will then be integrated by presenting approaches in which the effects of preload, afterload, and myocardial contractility can be examined. Moreover, the utility of the pressure-volume relation in terms of assessing both myocardial contractility as well as critical aspects of diastolic performance will be presented. Finally, a generalized approach for the assessment and interpretation of cardiac function within the intact cardiovascular system will be presented. Copyright © 2015 John Wiley & Sons, Inc.

  5. Assessment of density functional theory for bonds formed between rare gases and open-shell atoms: a computational study of small molecules containing He, Ar, Kr and Xe.

    Science.gov (United States)

    Bertolus, Marjorie; Major, Mohamed; Brenner, Valérie

    2012-01-14

    The validity of the description of the DFT approximations currently implemented in plane wave DFT codes (LDA, GGA, meta-GGA, hybrid, GGA + empirical dispersion correction) for interactions between rare gases and open-shell atoms which form materials is poorly known. We have performed a first assessment of the accuracy of these functionals for the description of the bonds formed by helium, argon, krypton and xenon with various open-shell atoms. This evaluation has been done on model molecular systems for which precise experimental data are available and reference post-Hartree-Fock calculations (CCSD(T) using large basis sets) are feasible. The results show that when the rare gas atom shares density with the neighbouring atoms, the GGA functionals yield good geometries and qualitatively correct binding energies, even if these are quite significantly overestimated. The use of hybrid functionals enables us to obtain good geometries and satisfactory binding energies. For compounds in which the rare gas atom forms weak dispersive-like bonding, the accuracy yielded by the various functionals is not as good. No functional gives satisfactory binding energies for all the compounds investigated. Several GGA and hybrid functionals yield correct geometries, even if some isomers are not obtained. One GGA functional (PBE) yields qualitatively correct results for the compounds of the three rare gases and several hybrid functionals give satisfactory energies for He compounds. The addition of an empirical dispersive correction improves the results on association compounds, but several isomers are not found.

  6. Assessment of density functional theory for bonds formed between rare gases and open-shell atoms: a computational study of small molecules containing He, Ar, Kr and Xe

    International Nuclear Information System (INIS)

    Bertolus, Marjorie; Major, Mohamed; Brenner, Valerie

    2012-01-01

    The validity of the description of the DFT approximations currently implemented in plane wave DFT codes (LDA, GGA, meta-GGA, hybrid, GGA + empirical dispersion correction) for interactions between rare gases and open-shell atoms which form materials is poorly known. We have performed a first assessment of the accuracy of these functionals for the description of the bonds formed by helium, argon, krypton and xenon with various open-shell atoms. This evaluation has been done on model molecular systems for which precise experimental data are available and reference post-Hartree-Fock calculations (CCSD(T) using large basis sets) are feasible. The results show that when the rare gas atom shares density with the neighbouring atoms, the GGA functionals yield good geometries and qualitatively correct binding energies, even if these are quite significantly overestimated. The use of hybrid functionals enables us to obtain good geometries and satisfactory binding energies. For compounds in which the rare gas atom forms weak dispersive-like bonding, the accuracy yielded by the various functionals is not as good. No functional gives satisfactory binding energies for all the compounds investigated. Several GGA and hybrid functionals yield correct geometries, even if some isomers are not obtained. One GGA functional (PBE) yields qualitatively correct results for the compounds of the three rare gases and several hybrid functionals give satisfactory energies for He compounds. The addition of an empirical dispersive correction improves the results on association compounds, but several isomers are not found. (authors)

  7. Transfer function approach to signal discrimination of ULF geomagnetic data

    Science.gov (United States)

    Harada, M.; Hattori, K.; Isezaki, N.

    In order to study earthquake-related ULF geomagnetic field changes, it is important to discriminate the noises such as magnetic pulsations originated from solar-terrestrial interactions and artificial noises from DC-driven trains and factories. For this aim, the interstation transfer functions and wavelet transform method have been proposed and applied to the data obtained at the ULF electromagnetic sensor array at the Boso Peninsula, Japan. It is concluded that this interstation transfer function approach has a capacity for signal discrimination; that is, it shows effectiveness to eliminate noises originated from the external ionospheric sources and its secondary effects.

  8. Green-function approach for scattering quantum walks

    Energy Technology Data Exchange (ETDEWEB)

    Andrade, F. M. [Departamento de Matematica e Estatistica, Universidade Estadual de Ponta Grossa, 84030-900 Ponta Grossa-PR (Brazil); Luz, M. G. E. da [Departamento de Fisica, Universidade Federal do Parana, C.P. 19044, 81531-980 Curitiba-PR (Brazil)

    2011-10-15

    In this work a Green-function approach for scattering quantum walks is developed. The exact formula has the form of a sum over paths and always can be cast into a closed analytic expression for arbitrary topologies and position-dependent quantum amplitudes. By introducing the step and path operators, it is shown how to extract any information about the system from the Green function. The method's relevant features are demonstrated by discussing in detail an example, a general diamond-shaped graph.

  9. Functional connectivity and brain activation: a synergistic approach.

    Science.gov (United States)

    Tomasi, Dardo; Wang, Ruiliang; Wang, Gene-Jack; Volkow, Nora D

    2014-10-01

    Traditional functional magnetic resonance imaging (fMRI) studies exploit endogenous brain activity for mapping brain activation during "periodic" cognitive/emotional challenges or brain functional connectivity during the "resting state". Previous studies demonstrated that these approaches provide a limited view of brain function which can be complemented by each other. We hypothesized that graph theory functional connectivity density (FCD) mapping would demonstrate regional FCD decreases between resting-state scan and a continuous "task-state" scan. Forty-five healthy volunteers underwent functional connectivity MRI during resting-state as well as a continuous visual attention task, and standard fMRI with a blocked version of the visual attention task. High-resolution data-driven FCD mapping was used to measure task-related connectivity changes without a priori hypotheses. Results demonstrate that task performance was associated with FCD decreases in brain regions weakly activated/deactivated by the task. Furthermore, a pronounced negative correlation between blood oxygen level-dependent-fMRI activation and task-related FCD decreases emerged across brain regions that also suggest the disconnection of task-irrelevant networks during task performance. The correlation between improved accuracy and stronger FCD decreases further suggests the disconnection of task-irrelevant networks during task performance. Functional connectivity can potentiate traditional fMRI studies and offer a more complete picture of brain function. Published by Oxford University Press 2013. This work is written by (a) US Government employee(s) and is in the public domain in the US.

  10. New approach to equipment quality evaluation method with distinct functions

    Directory of Open Access Journals (Sweden)

    Milisavljević Vladimir M.

    2016-01-01

    Full Text Available The paper presents new approach for improving method for quality evaluation and selection of equipment (devices and machinery by applying distinct functions. Quality evaluation and selection of devices and machinery is a multi-criteria problem which involves the consideration of numerous parameters of various origins. Original selection method with distinct functions is based on technical parameters with arbitrary evaluation of each parameter importance (weighting. Improvement of this method, presented in this paper, addresses the issue of weighting of parameters by using Delphi Method. Finally, two case studies are provided, which included quality evaluation of standard boilers for heating and evaluation of load-haul-dump (LHD machines, to demonstrate applicability of this approach. Analytical Hierarchical Process (AHP is used as a control method.

  11. A minimalist functional group (MFG) approach for surrogate fuel formulation

    KAUST Repository

    Abdul Jameel, Abdul Gani

    2018-03-20

    Surrogate fuel formulation has drawn significant interest due to its relevance towards understanding combustion properties of complex fuel mixtures. In this work, we present a novel approach for surrogate fuel formulation by matching target fuel functional groups, while minimizing the number of surrogate species. Five key functional groups; paraffinic CH, paraffinic CH, paraffinic CH, naphthenic CH–CH and aromatic C–CH groups in addition to structural information provided by the Branching Index (BI) were chosen as matching targets. Surrogates were developed for six FACE (Fuels for Advanced Combustion Engines) gasoline target fuels, namely FACE A, C, F, G, I and J. The five functional groups present in the fuels were qualitatively and quantitatively identified using high resolution H Nuclear Magnetic Resonance (NMR) spectroscopy. A further constraint was imposed in limiting the number of surrogate components to a maximum of two. This simplifies the process of surrogate formulation, facilitates surrogate testing, and significantly reduces the size and time involved in developing chemical kinetic models by reducing the number of thermochemical and kinetic parameters requiring estimation. Fewer species also reduces the computational expenses involved in simulating combustion in practical devices. The proposed surrogate formulation methodology is denoted as the Minimalist Functional Group (MFG) approach. The MFG surrogates were experimentally tested against their target fuels using Ignition Delay Times (IDT) measured in an Ignition Quality Tester (IQT), as specified by the standard ASTM D6890 methodology, and in a Rapid Compression Machine (RCM). Threshold Sooting Index (TSI) and Smoke Point (SP) measurements were also performed to determine the sooting propensities of the surrogates and target fuels. The results showed that MFG surrogates were able to reproduce the aforementioned combustion properties of the target FACE gasolines across a wide range of conditions

  12. A Goal-Function Approach to Analysis of Control Situations

    DEFF Research Database (Denmark)

    Lind, Morten

    2010-01-01

    processes situations should identify operational aspects relevant for control agent’s decision making in plant supervision and control. Control situations can be understood as recurrent and interconnected patterns of control with important implications for control and HMI design. Goal-Function approaches...... to systems modeling like Multilevel Flow Modeling can be used to represent control situations. The paper will describe an action theoretical foundation for MFM and its use for the development of a theory of control situations....

  13. A zeta function approach to the semiclassical quantization of maps

    International Nuclear Information System (INIS)

    Smilansky, Uzi.

    1993-11-01

    The quantum analogue of an area preserving map on a compact phase space is a unitary (evolution) operator which can be represented by a matrix of dimension L∝ℎ -1 . The semiclassical theory for spectrum of the evolution operator will be reviewed with special emphasize on developing a dynamical zeta function approach, similar to the one introduced recently for a semiclassical quantization of hamiltonian systems. (author)

  14. A chiral organic base catalyst with halogen-bonding-donor functionality: asymmetric Mannich reactions of malononitrile with N-Boc aldimines and ketimines.

    Science.gov (United States)

    Kuwano, Satoru; Suzuki, Takumi; Hosaka, Yusei; Arai, Takayoshi

    2018-03-29

    A chiral organic base catalyst with halogen-bonding-donor functionality has been developed. This quinidine-derived acid/base catalyst smoothly promoted the asymmetric Mannich reaction of malononitrile and various N-Boc imines with up to 98% ee. The cooperative interaction with both substrates was responsible for the high activity that allowed a reduction of the catalyst amount to 0.5 mol%.

  15. Functional Foods and Lifestyle Approaches for Diabetes Prevention and Management.

    Science.gov (United States)

    Alkhatib, Ahmad; Tsang, Catherine; Tiss, Ali; Bahorun, Theeshan; Arefanian, Hossein; Barake, Roula; Khadir, Abdelkrim; Tuomilehto, Jaakko

    2017-12-01

    Functional foods contain biologically active ingredients associated with physiological health benefits for preventing and managing chronic diseases, such as type 2 diabetes mellitus (T2DM). A regular consumption of functional foods may be associated with enhanced anti-oxidant, anti-inflammatory, insulin sensitivity, and anti-cholesterol functions, which are considered integral to prevent and manage T2DM. Components of the Mediterranean diet (MD)-such as fruits, vegetables, oily fish, olive oil, and tree nuts-serve as a model for functional foods based on their natural contents of nutraceuticals, including polyphenols, terpenoids, flavonoids, alkaloids, sterols, pigments, and unsaturated fatty acids. Polyphenols within MD and polyphenol-rich herbs-such as coffee, green tea, black tea, and yerba maté-have shown clinically-meaningful benefits on metabolic and microvascular activities, cholesterol and fasting glucose lowering, and anti-inflammation and anti-oxidation in high-risk and T2DM patients. However, combining exercise with functional food consumption can trigger and augment several metabolic and cardiovascular protective benefits, but it is under-investigated in people with T2DM and bariatric surgery patients. Detecting functional food benefits can now rely on an "omics" biological profiling of individuals' molecular, genetics, transcriptomics, proteomics, and metabolomics, but is under-investigated in multi-component interventions. A personalized approach for preventing and managing T2DM should consider biological and behavioral models, and embed nutrition education as part of lifestyle diabetes prevention studies. Functional foods may provide additional benefits in such an approach.

  16. Functional Foods and Lifestyle Approaches for Diabetes Prevention and Management

    Directory of Open Access Journals (Sweden)

    Ahmad Alkhatib

    2017-12-01

    Full Text Available Functional foods contain biologically active ingredients associated with physiological health benefits for preventing and managing chronic diseases, such as type 2 diabetes mellitus (T2DM. A regular consumption of functional foods may be associated with enhanced anti-oxidant, anti-inflammatory, insulin sensitivity, and anti-cholesterol functions, which are considered integral to prevent and manage T2DM. Components of the Mediterranean diet (MD—such as fruits, vegetables, oily fish, olive oil, and tree nuts—serve as a model for functional foods based on their natural contents of nutraceuticals, including polyphenols, terpenoids, flavonoids, alkaloids, sterols, pigments, and unsaturated fatty acids. Polyphenols within MD and polyphenol-rich herbs—such as coffee, green tea, black tea, and yerba maté—have shown clinically-meaningful benefits on metabolic and microvascular activities, cholesterol and fasting glucose lowering, and anti-inflammation and anti-oxidation in high-risk and T2DM patients. However, combining exercise with functional food consumption can trigger and augment several metabolic and cardiovascular protective benefits, but it is under-investigated in people with T2DM and bariatric surgery patients. Detecting functional food benefits can now rely on an “omics” biological profiling of individuals’ molecular, genetics, transcriptomics, proteomics, and metabolomics, but is under-investigated in multi-component interventions. A personalized approach for preventing and managing T2DM should consider biological and behavioral models, and embed nutrition education as part of lifestyle diabetes prevention studies. Functional foods may provide additional benefits in such an approach.

  17. Tensor function approach to constitutive equations of inelasticity

    International Nuclear Information System (INIS)

    Murakami, S.

    1979-01-01

    Though various theories for elaborated engineering constitutive models have been proposed so far to improve the description of inelastic response of engineering materials, most of them have been formulated within the framework of the classical theories of plasticity and creep. In these cases, the expressions of flow potentials and hardening rules are usually modified a priori by adding some additional terms, and the related material constants are determined by experiments. The difficulties of such approaches consist in the lack of generality and pertinence, besides that they are considerably laborious. In the field of non-linear continuum mechanics, on the other hand, there has been a continuos development of more powerful approaches which are applicable to these problems. It is the aim of the present paper to show the utility of the tensor function approach to the development of the non-classical constitutive equations of inelasticity and to elucidate the practical procedures and some new results of it. (orig.)

  18. Fuzzy set approach to quality function deployment: An investigation

    Science.gov (United States)

    Masud, Abu S. M.

    1992-01-01

    The final report of the 1992 NASA/ASEE Summer Faculty Fellowship at the Space Exploration Initiative Office (SEIO) in Langley Research Center is presented. Quality Function Deployment (QFD) is a process, focused on facilitating the integration of the customer's voice in the design and development of a product or service. Various input, in the form of judgements and evaluations, are required during the QFD analyses. All the input variables in these analyses are treated as numeric variables. The purpose of the research was to investigate how QFD analyses can be performed when some or all of the input variables are treated as linguistic variables with values expressed as fuzzy numbers. The reason for this consideration is that human judgement, perception, and cognition are often ambiguous and are better represented as fuzzy numbers. Two approaches for using fuzzy sets in QFD have been proposed. In both cases, all the input variables are considered as linguistic variables with values indicated as linguistic expressions. These expressions are then converted to fuzzy numbers. The difference between the two approaches is due to how the QFD computations are performed with these fuzzy numbers. In Approach 1, the fuzzy numbers are first converted to their equivalent crisp scores and then the QFD computations are performed using these crisp scores. As a result, the output of this approach are crisp numbers, similar to those in traditional QFD. In Approach 2, all the QFD computations are performed with the fuzzy numbers and the output are fuzzy numbers also. Both the approaches have been explained with the help of illustrative examples of QFD application. Approach 2 has also been applied in a QFD application exercise in SEIO, involving a 'mini moon rover' design. The mini moon rover is a proposed tele-operated vehicle that will traverse and perform various tasks, including autonomous operations, on the moon surface. The output of the moon rover application exercise is a

  19. Novel approaches in function-driven single-cell genomics.

    Science.gov (United States)

    Doud, Devin F R; Woyke, Tanja

    2017-07-01

    Deeper sequencing and improved bioinformatics in conjunction with single-cell and metagenomic approaches continue to illuminate undercharacterized environmental microbial communities. This has propelled the 'who is there, and what might they be doing' paradigm to the uncultivated and has already radically changed the topology of the tree of life and provided key insights into the microbial contribution to biogeochemistry. While characterization of 'who' based on marker genes can describe a large fraction of the community, answering 'what are they doing' remains the elusive pinnacle for microbiology. Function-driven single-cell genomics provides a solution by using a function-based screen to subsample complex microbial communities in a targeted manner for the isolation and genome sequencing of single cells. This enables single-cell sequencing to be focused on cells with specific phenotypic or metabolic characteristics of interest. Recovered genomes are conclusively implicated for both encoding and exhibiting the feature of interest, improving downstream annotation and revealing activity levels within that environment. This emerging approach has already improved our understanding of microbial community functioning and facilitated the experimental analysis of uncharacterized gene product space. Here we provide a comprehensive review of strategies that have been applied for function-driven single-cell genomics and the future directions we envision. © FEMS 2017.

  20. Zeta-function approach to Casimir energy with singular potentials

    International Nuclear Information System (INIS)

    Khusnutdinov, Nail R.

    2006-01-01

    In the framework of zeta-function approach the Casimir energy for three simple model system: single delta potential, step function potential and three delta potentials are analyzed. It is shown that the energy contains contributions which are peculiar to the potentials. It is suggested to renormalize the energy using the condition that the energy of infinitely separated potentials is zero which corresponds to subtraction all terms of asymptotic expansion of zeta-function. The energy obtained in this way obeys all physically reasonable conditions. It is finite in the Dirichlet limit, and it may be attractive or repulsive depending on the strength of potential. The effective action is calculated, and it is shown that the surface contribution appears. The renormalization of the effective action is discussed

  1. Moment generating function approach to pricing interest rate and foreign exchange rate claims

    NARCIS (Netherlands)

    Dijkstra, T.K.; Yao, Y.

    2002-01-01

    This paper uses moment generating functions to provide a general framework to model international term structures and to price interest rate and foreign exchange rate claims. When moment generating functions of state variables have a closed-form formula, closed-form formulas for bond prices are

  2. Number series of atoms, interatomic bonds and interface bonds defining zinc-blende nanocrystals as function of size, shape and surface orientation: Analytic tools to interpret solid state spectroscopy data

    International Nuclear Information System (INIS)

    König, Dirk

    2016-01-01

    Semiconductor nanocrystals (NCs) experience stress and charge transfer by embedding materials or ligands and impurity atoms. In return, the environment of NCs experiences a NC stress response which may lead to matrix deformation and propagated strain. Up to now, there is no universal gauge to evaluate the stress impact on NCs and their response as a function of NC size d NC . I deduce geometrical number series as analytical tools to obtain the number of NC atoms N NC (d NC [i]), bonds between NC atoms N bnd (d NC [i]) and interface bonds N IF (d NC [i]) for seven high symmetry zinc-blende (zb) NCs with low-index faceting: {001} cubes, {111} octahedra, {110} dodecahedra, {001}-{111} pyramids, {111} tetrahedra, {111}-{001} quatrodecahedra and {001}-{111} quadrodecahedra. The fundamental insights into NC structures revealed here allow for major advancements in data interpretation and understanding of zb- and diamond-lattice based nanomaterials. The analytical number series can serve as a standard procedure for stress evaluation in solid state spectroscopy due to their deterministic nature, easy use and general applicability over a wide range of spectroscopy methods as well as NC sizes, forms and materials.

  3. The unique functional role of the C-HS hydrogen bond in the substrate specificity and enzyme catalysis of type 1 methionine aminopeptidase.

    Science.gov (United States)

    Reddi, Ravikumar; Singarapu, Kiran Kumar; Pal, Debnath; Addlagatta, Anthony

    2016-07-19

    It is intriguing how nature attains recognition specificity between molecular interfaces where there is no apparent scope for classical hydrogen bonding or polar interactions. Methionine aminopeptidase (MetAP) is one such enzyme where this fascinating conundrum is at play. In this study, we demonstrate that a unique C-HS hydrogen bond exists between the enzyme methionine aminopeptidase (MetAP) and its N-terminal-methionine polypeptide substrate, which allows specific interaction between apparent apolar interfaces, imposing a strict substrate recognition specificity and efficient catalysis, a feature replicated in Type I MetAPs across all kingdoms of life. We evidence this evolutionarily conserved C-HS hydrogen bond through enzyme assays on wild-type and mutant MetAP proteins from Mycobacterium tuberculosis that show a drastic difference in catalytic efficiency. The X-ray crystallographic structure of the methionine bound protein revealed a conserved water bridge and short contacts involving the Met side-chain, a feature also observed in MetAPs from other organisms. Thermal shift assays showed a remarkable 3.3 °C increase in melting temperature for methionine bound protein compared to its norleucine homolog, where C-HS interaction is absent. The presence of C-HS hydrogen bonding was also corroborated by nuclear magnetic resonance spectroscopy through a change in chemical shift. Computational chemistry studies revealed the unique role of the electrostatic environment in facilitating the C-HS interaction. The significance of this atypical hydrogen bond is underscored by the fact that the function of MetAP is essential for any living cell.

  4. Physiotherapeutic approach and functional performance after breast cancer surgery

    Directory of Open Access Journals (Sweden)

    Mariana Tirolli Rett

    Full Text Available Abstract Introduction: Surgery for breast cancer can impair range of motion (ROM and functionality of upper limb (UL. Objective: To compare ROM and functional performance of homolateral UL after physiotherapeutic approach and to correlate these variables. Methods: A non-randomized clinical trial study enrolled 33 women who were submitted to mastectomy or quadrantectomy associated with axillary lymphadenectomy. ROM was assessed by homolateral UL and contralateral limb (control goniometry. Functional performance was assessed by “Disability of arm, shoulder and hand” (DASH questionnaire. The protocol consisted in 10 sessions (3 sessions per week during 60 minutes, involving passive mobilization of glenohumeral and scapulothoracic joint, soft tissue mobilization, neck muscles and upper limb muscles stretching, exercises in all planes of motion, applied alone or in combination. Weight bearing exercise with elastic bands and dumbbells from 0.5 to 1.0 kilograms were also applied. Results: There was a meaningful increase in ROM of all movements after physiotherapy; however, flexion, abduction and lateral rotation remained lower than control limb. DASH score decreased significantly from 28.06 ± 16.1 to 15.71 ± 10.7 (p = 0.001 meaning an improvement in functional performance of UL. No correlation was observed between ROM and DASH. Conclusion: Functional performance and ROM, after 10 physiotherapy sessions, improved significantly, however, a long-term follow-up can contribute to further improvement.

  5. Correlation functions of the spin chains. Algebraic Bethe Ansatz approach

    International Nuclear Information System (INIS)

    Kitanine, N.

    2007-09-01

    Spin chains are the basic elements of integrable quantum models. These models have direct applications in condense matter theory, in statistical physics, in quantum optics, in field theory and even in string theory but they are also important because they enable us to solve, in an exact manner, non-perturbative phenomena that otherwise would stay unresolved. The method described in this work is based on the algebraic Bethe Ansatz. It is shown how this method can be used for the computation of null temperature correlation functions of the Heisenberg 1/2 spin chain. The important point of this approach is the solution of the inverse quantum problem given by the XXZ spin chain. This solution as well as a simple formulae for the scalar product of the Bethe states, have enabled us to get the most basic correlation functions under the form of multiple integrals. The formalism of multiple integrals open the way for asymptotic analysis for a few physical quantities like the probability of vacuum formation. It is worth noticing that this formalism can give exact results for two-point functions that are the most important correlation functions for applications. A relationship has been discovered between these multiple integrals and the sum of the form factors. The results have been extended to dynamical correlation functions. (A.C.)

  6. Dynamic modelling of the expansion cylinder of an open Joule cycle Ericsson engine: A bond graph approach

    International Nuclear Information System (INIS)

    Creyx, M.; Delacourt, E.; Morin, C.; Desmet, B.

    2016-01-01

    A dynamic model using the bond graph formalism of the expansion cylinder of an open Joule cycle Ericsson engine intended for a biomass-fuelled micro-CHP system is presented. Dynamic phenomena, such as the thermodynamic evolution of air, the instantaneous air mass flow rates linked to pressure drops crossing the valves, the heat transferred through the expansion cylinder wall and the mechanical friction losses, are included in the model. The influence on the Ericsson engine performances of the main operating conditions (intake air pressure and temperature, timing of intake and exhaust valve closing, rotational speed, mechanical friction losses and heat transfer at expansion cylinder wall) is studied. The operating conditions maximizing the performances of the Ericsson engine used in the a biomass-fuelled micro-CHP unit are an intake air pressure between 6 and 8 bar, a maximized intake air temperature, an adjustment of the intake and exhaust valve closing corresponding to an expansion cycle close to the theoretical Joule cycle, a rotational speed close to 800 rpm. The heat transfer at the expansion cylinder wall reduces the engine performances. - Highlights: • A bond graph dynamic model of the Ericsson engine expansion cylinder is presented. • Dynamic aspects are modelled: pressure drops, friction losses, wall heat transfer. • Influent factors and phenomena on the engine performances are investigated. • Expansion cycles close to the theoretical Joule cycle maximize the performances. • The heat transfer at the expansion chamber wall reduces the performances.

  7. Dual Approach to the Study of Land Market Functioning

    Directory of Open Access Journals (Sweden)

    Liliya Oganesovna Oganesyan

    2015-12-01

    Full Text Available The article reveals the essence, the structural elements and features of the mechanism of functioning of the market of agricultural land. The authors present the supplementing idea on the structural dichotomy of the agricultural land market. In contrast to neoclassical approaches, it is proposed to explore the market based on its structural dichotomy – market property rights and market rights of management. In this context, the mechanism of functioning of agricultural lands market performs the function of a basic element in the system of land relations to ensure market circulation of agricultural land through alienation and assign full or partial rights of land ownership. The use of the institutional approach to the study of market structures justifies the dual nature of the mechanism of functioning of the market of agricultural land due to the fact that on the one hand, the market is slow and limited in the market space of the rare economic good or factor of production, and on the other hand, it is a dynamic institutional and economic system within which the specification of property rights to land is implemented. The structure of the mechanism of functioning and development of agricultural land market is considered as a system of interrelated and interacting elements of state regulation and market self-regulation, based on the principles of coordination and harmonization of personalized economic interests and market law of supply and demand. The combination of elements of market self-regulation and state regulation allows in practice to justify the choice of model combinations of stable and changing elements of the mechanism. This combination complies with the institutional conditions for the functioning of the market of agricultural land considering the dominance of regulated sustainable standards at the market of property rights and in the frames of informal institutions at the market of the management rights. The authors prove the

  8. Excitation energies with linear response density matrix functional theory along the dissociation coordinate of an electron-pair bond in N-electron systems

    International Nuclear Information System (INIS)

    Meer, R. van; Gritsenko, O. V.; Baerends, E. J.

    2014-01-01

    Time dependent density matrix functional theory in its adiabatic linear response formulation delivers exact excitation energies ω α and oscillator strengths f α for two-electron systems if extended to the so-called phase including natural orbital (PINO) theory. The Löwdin-Shull expression for the energy of two-electron systems in terms of the natural orbitals and their phases affords in this case an exact phase-including natural orbital functional (PILS), which is non-primitive (contains other than just J and K integrals). In this paper, the extension of the PILS functional to N-electron systems is investigated. With the example of an elementary primitive NO functional (BBC1) it is shown that current density matrix functional theory ground state functionals, which were designed to produce decent approximations to the total energy, fail to deliver a qualitatively correct structure of the (inverse) response function, due to essential deficiencies in the reconstruction of the two-body reduced density matrix (2RDM). We now deduce essential features of an N-electron functional from a wavefunction Ansatz: The extension of the two-electron Löwdin-Shull wavefunction to the N-electron case informs about the phase information. In this paper, applications of this extended Löwdin-Shull (ELS) functional are considered for the simplest case, ELS(1): one (dissociating) two-electron bond in the field of occupied (including core) orbitals. ELS(1) produces high quality ω α (R) curves along the bond dissociation coordinate R for the molecules LiH, Li 2 , and BH with the two outer valence electrons correlated. All of these results indicate that response properties are much more sensitive to deficiencies in the reconstruction of the 2RDM than the ground state energy, since derivatives of the functional with respect to both the NOs and the occupation numbers need to be accurate

  9. Sensorimotor integration for functional recovery and the Bobath approach.

    Science.gov (United States)

    Levin, Mindy F; Panturin, Elia

    2011-04-01

    Bobath therapy is used to treat patients with neurological disorders. Bobath practitioners use hands-on approaches to elicit and reestablish typical movement patterns through therapist-controlled sensorimotor experiences within the context of task accomplishment. One aspect of Bobath practice, the recovery of sensorimotor function, is reviewed within the framework of current motor control theories. We focus on the role of sensory information in movement production, the relationship between posture and movement and concepts related to motor recovery and compensation with respect to this therapeutic approach. We suggest that a major barrier to the evaluation of the therapeutic effectiveness of the Bobath concept is the lack of a unified framework for both experimental identification and treatment of neurological motor deficits. More conclusive analysis of therapeutic effectiveness requires the development of specific outcomes that measure movement quality.

  10. Optimal Investment in Structured Bonds

    DEFF Research Database (Denmark)

    Jessen, Pernille; Jørgensen, Peter Løchte

    The paper examines the role of structured bonds in the optimal portfolio of a small retail investor. We consider the typical structured bond essentially repacking an exotic option and a zero coupon bond, i.e. an investment with portfolio insurance. The optimal portfolio is found when the investment...... opportunities consist of a risky reference fund, a risk-free asset and a structured bond. Key model elements are the trading strategy and utility function of the investor. Our numerical results indicate structured bonds do have basis for consideration in the optimal portfolio. The product holdings...

  11. Developmental Programming of Renal Function and Re-Programming Approaches.

    Science.gov (United States)

    Nüsken, Eva; Dötsch, Jörg; Weber, Lutz T; Nüsken, Kai-Dietrich

    2018-01-01

    Chronic kidney disease affects more than 10% of the population. Programming studies have examined the interrelationship between environmental factors in early life and differences in morbidity and mortality between individuals. A number of important principles has been identified, namely permanent structural modifications of organs and cells, long-lasting adjustments of endocrine regulatory circuits, as well as altered gene transcription. Risk factors include intrauterine deficiencies by disturbed placental function or maternal malnutrition, prematurity, intrauterine and postnatal stress, intrauterine and postnatal overnutrition, as well as dietary dysbalances in postnatal life. This mini-review discusses critical developmental periods and long-term sequelae of renal programming in humans and presents studies examining the underlying mechanisms as well as interventional approaches to "re-program" renal susceptibility toward disease. Clinical manifestations of programmed kidney disease include arterial hypertension, proteinuria, aggravation of inflammatory glomerular disease, and loss of kidney function. Nephron number, regulation of the renin-angiotensin-aldosterone system, renal sodium transport, vasomotor and endothelial function, myogenic response, and tubuloglomerular feedback have been identified as being vulnerable to environmental factors. Oxidative stress levels, metabolic pathways, including insulin, leptin, steroids, and arachidonic acid, DNA methylation, and histone configuration may be significantly altered by adverse environmental conditions. Studies on re-programming interventions focused on dietary or anti-oxidative approaches so far. Further studies that broaden our understanding of renal programming mechanisms are needed to ultimately develop preventive strategies. Targeted re-programming interventions in animal models focusing on known mechanisms will contribute to new concepts which finally will have to be translated to human application. Early

  12. Developmental Programming of Renal Function and Re-Programming Approaches

    Directory of Open Access Journals (Sweden)

    Eva Nüsken

    2018-02-01

    Full Text Available Chronic kidney disease affects more than 10% of the population. Programming studies have examined the interrelationship between environmental factors in early life and differences in morbidity and mortality between individuals. A number of important principles has been identified, namely permanent structural modifications of organs and cells, long-lasting adjustments of endocrine regulatory circuits, as well as altered gene transcription. Risk factors include intrauterine deficiencies by disturbed placental function or maternal malnutrition, prematurity, intrauterine and postnatal stress, intrauterine and postnatal overnutrition, as well as dietary dysbalances in postnatal life. This mini-review discusses critical developmental periods and long-term sequelae of renal programming in humans and presents studies examining the underlying mechanisms as well as interventional approaches to “re-program” renal susceptibility toward disease. Clinical manifestations of programmed kidney disease include arterial hypertension, proteinuria, aggravation of inflammatory glomerular disease, and loss of kidney function. Nephron number, regulation of the renin–angiotensin–aldosterone system, renal sodium transport, vasomotor and endothelial function, myogenic response, and tubuloglomerular feedback have been identified as being vulnerable to environmental factors. Oxidative stress levels, metabolic pathways, including insulin, leptin, steroids, and arachidonic acid, DNA methylation, and histone configuration may be significantly altered by adverse environmental conditions. Studies on re-programming interventions focused on dietary or anti-oxidative approaches so far. Further studies that broaden our understanding of renal programming mechanisms are needed to ultimately develop preventive strategies. Targeted re-programming interventions in animal models focusing on known mechanisms will contribute to new concepts which finally will have to be translated

  13. Developmental Programming of Renal Function and Re-Programming Approaches

    Science.gov (United States)

    Nüsken, Eva; Dötsch, Jörg; Weber, Lutz T.; Nüsken, Kai-Dietrich

    2018-01-01

    Chronic kidney disease affects more than 10% of the population. Programming studies have examined the interrelationship between environmental factors in early life and differences in morbidity and mortality between individuals. A number of important principles has been identified, namely permanent structural modifications of organs and cells, long-lasting adjustments of endocrine regulatory circuits, as well as altered gene transcription. Risk factors include intrauterine deficiencies by disturbed placental function or maternal malnutrition, prematurity, intrauterine and postnatal stress, intrauterine and postnatal overnutrition, as well as dietary dysbalances in postnatal life. This mini-review discusses critical developmental periods and long-term sequelae of renal programming in humans and presents studies examining the underlying mechanisms as well as interventional approaches to “re-program” renal susceptibility toward disease. Clinical manifestations of programmed kidney disease include arterial hypertension, proteinuria, aggravation of inflammatory glomerular disease, and loss of kidney function. Nephron number, regulation of the renin–angiotensin–aldosterone system, renal sodium transport, vasomotor and endothelial function, myogenic response, and tubuloglomerular feedback have been identified as being vulnerable to environmental factors. Oxidative stress levels, metabolic pathways, including insulin, leptin, steroids, and arachidonic acid, DNA methylation, and histone configuration may be significantly altered by adverse environmental conditions. Studies on re-programming interventions focused on dietary or anti-oxidative approaches so far. Further studies that broaden our understanding of renal programming mechanisms are needed to ultimately develop preventive strategies. Targeted re-programming interventions in animal models focusing on known mechanisms will contribute to new concepts which finally will have to be translated to human application

  14. Matrix converter controlled with the direct transfer function approach

    DEFF Research Database (Denmark)

    Rodriguez, J.; Silva, E.; Blaabjerg, Frede

    2005-01-01

    Power electronics is an emerging technology. New power circuits are invented and have to be introduced into the power electronics curriculum. One of the interesting new circuits is the matrix converter (MC), and this paper analyses its working principles. A simple model is proposed to represent...... the power circuit, including the input filter. The power semiconductors are modelled as ideal bidirectional switches and the MC is controlled using a direct transfer function approach. The modulation strategy of the converter is explained in a complete and clear form. The commutation problem of two switches...

  15. A Model-Based Approach to Constructing Music Similarity Functions

    Science.gov (United States)

    West, Kris; Lamere, Paul

    2006-12-01

    Several authors have presented systems that estimate the audio similarity of two pieces of music through the calculation of a distance metric, such as the Euclidean distance, between spectral features calculated from the audio, related to the timbre or pitch of the signal. These features can be augmented with other, temporally or rhythmically based features such as zero-crossing rates, beat histograms, or fluctuation patterns to form a more well-rounded music similarity function. It is our contention that perceptual or cultural labels, such as the genre, style, or emotion of the music, are also very important features in the perception of music. These labels help to define complex regions of similarity within the available feature spaces. We demonstrate a machine-learning-based approach to the construction of a similarity metric, which uses this contextual information to project the calculated features into an intermediate space where a music similarity function that incorporates some of the cultural information may be calculated.

  16. The Use of Modeling Approach for Teaching Exponential Functions

    Science.gov (United States)

    Nunes, L. F.; Prates, D. B.; da Silva, J. M.

    2017-12-01

    This work presents a discussion related to the teaching and learning of mathematical contents related to the study of exponential functions in a freshman students group enrolled in the first semester of the Science and Technology Bachelor’s (STB of the Federal University of Jequitinhonha and Mucuri Valleys (UFVJM). As a contextualization tool strongly mentioned in the literature, the modelling approach was used as an educational teaching tool to produce contextualization in the teaching-learning process of exponential functions to these students. In this sense, were used some simple models elaborated with the GeoGebra software and, to have a qualitative evaluation of the investigation and the results, was used Didactic Engineering as a methodology research. As a consequence of this detailed research, some interesting details about the teaching and learning process were observed, discussed and described.

  17. The Navier-Stokes equations an elementary functional analytic approach

    CERN Document Server

    Sohr, Hermann

    2001-01-01

    The primary objective of this monograph is to develop an elementary and self­ contained approach to the mathematical theory of a viscous incompressible fluid in a domain 0 of the Euclidean space ]Rn, described by the equations of Navier­ Stokes. The book is mainly directed to students familiar with basic functional analytic tools in Hilbert and Banach spaces. However, for readers' convenience, in the first two chapters we collect without proof some fundamental properties of Sobolev spaces, distributions, operators, etc. Another important objective is to formulate the theory for a completely general domain O. In particular, the theory applies to arbitrary unbounded, non-smooth domains. For this reason, in the nonlinear case, we have to restrict ourselves to space dimensions n = 2,3 that are also most significant from the physical point of view. For mathematical generality, we will develop the lin­ earized theory for all n 2 2. Although the functional-analytic approach developed here is, in principle, known ...

  18. Optimal Approaches for Measuring Tongue-Pressure Functional Reserve

    Directory of Open Access Journals (Sweden)

    Catriona M. Steele

    2013-01-01

    Full Text Available Tongue-palate pressure is a parameter of considerable interest in the field of dysphagia. Maximum isometric tongue-palate pressures (MIPs decline in healthy aging and in dysphagia. Functional reserve (FR is the difference between MIPs and swallowing pressures. Reduced FR is thought to constitute a risk for developing functional swallowing impairments. We compare different approaches for calculating FR and recommend an optimal approach. Tongue-palate pressure data were collected from 78 healthy adults (4060 during anterior and posterior MIPs, regular (RESS and effortful (ESS saliva swallows, and water swallows (4 repetitions per task. Six different measures of reserve were calculated using maximum anterior MIPs or ESS pressures at the top, and mean or maximum RESS or water swallow pressures at the bottom of the range. Correlations with age and MIPs were explored to confirm suitability for measuring FR. The impact of normalization to maximum MIP range was explored. We conclude that an optimal measure of FR involves the comparison of maximum MIP with mean saliva swallowing pressures. This parameter declines with age, but when normalized to an individual’s MIP range, the relationship is no longer evident. This suggests that FR does not necessarily decline in healthy aging.

  19. C–H Bonds as Ubiquitous Functionality: Preparation of Multiple Regioisomers of Arylated 1,2,4-Triazoles via C–H Arylation

    Science.gov (United States)

    Joo, Jung Min; Guo, Pengfei

    2013-01-01

    We describe a general approach for the synthesis of complex aryl 1,2,4-triazoles. The electronic character of the C–H bonds and the triazole ring allows for the regioselective C–H arylation of 1-alkyl and 4-alkyl triazoles under catalytic conditions. We have also developed the SEM- and THP-switch as well as trans-N-alkylation, which enable sequential arylation of the triazole ring to prepare 3,5-diaryltriazoles. This straightforward strategy provides rapid access to a variety of arylated 1,2,4-triazoles and well complements existing cyclization methods. PMID:23276283

  20. Can QTAIM topological parameters be a measure of hydrogen bonding strength?

    Science.gov (United States)

    Mo, Yirong

    2012-05-31

    The block-localized wave function (BLW) method, which is the simplest variant of ab initio valence bond (VB) theory, together with the quantum theory of atoms in molecules (QTAIM) approach, have been used to probe the intramolecular hydrogen bonding interactions in a series of representative systems of resonance-assisted hydrogen bonds (RAHBs). RAHB is characteristic of the cooperativity between the π-electron delocalization and hydrogen bonding interactions and is identified in many biological systems. While the deactivation of the π resonance in these RAHB systems by the use of the BLW method is expected to considerably weaken the hydrogen bonding strength, little change on the topological properties of electron densities at hydrogen bond critical points (HBCPs) is observed. This raises a question of whether the QTAIM topological parameters can be an effective measure of hydrogen bond strength.

  1. Finite frequency Seebeck coefficient of metals: A memory function approach

    Science.gov (United States)

    Bhalla, Pankaj; Kumar, Pradeep; Das, Nabyendu; Singh, Navinder

    2017-10-01

    We study the dynamical thermoelectric transport in metals subjected to the electron-impurity and the electron-phonon interactions using the memory function formalism. We introduce a generalized Drude form for the Seebeck coefficient in terms of thermoelectric memory function and calculate the latter in various temperature and frequency limits. In the zero frequency and high temperature limit, we find that our results are consistent with the experimental findings and with the traditional Boltzmann equation approach. In the low temperature limit, we find that the Seebeck coefficient is quadratic in temperature. In the finite frequency regime, we report new results: In the electron-phonon interaction case, we find that the Seebeck coefficient shows frequency independent behavior both in the high frequency regime (ω ≫ωD , where ωD is the Debye frequency) and in the low frequency regime (ω ≪ωD), whereas in the intermediate frequencies, it is a monotonically increasing function of frequency. In the case of the electron-impurity interaction, first it decays and then after passing through a minimum it increases with the increase in frequency and saturates at high frequencies.

  2. Pediatrician's knowledge on the approach of functional constipation.

    Science.gov (United States)

    Vieira, Mario C; Negrelle, Isadora Carolina Krueger; Webber, Karla Ulaf; Gosdal, Marjorie; Truppel, Sabine Krüger; Kusma, Solena Ziemer

    2016-12-01

    To evaluate the pediatrician's knowledge regarding the diagnostic and therapeutic approach of childhood functional constipation. A descriptive cross-sectional study was performed with the application of a self-administered questionnaire concerning a hypothetical clinical case of childhood functional constipation with fecal incontinence to physicians (n=297) randomly interviewed at the 36th Brazilian Congress of Pediatrics in 2013. The majority of the participants were females, the mean age was 44.1 years, the mean time of professional practice was 18.8 years; 56.9% were Board Certified by the Brazilian Society of Pediatrics. Additional tests were ordered by 40.4%; including abdominal radiography (19.5%), barium enema (10.4%), laboratory tests (9.8%), abdominal ultrasound (6.7%), colonoscopy (2.4%), manometry and rectal biopsy (both 1.7%). The most common interventions included lactulose (26.6%), mineral oil (17.5%), polyethylene glycol (14.5%), fiber supplement (9.1%) and milk of magnesia (5.4%). Nutritional guidance (84.8%), fecal disimpaction (17.2%) and toilet training (19.5%) were also indicated. Our results show that pediatricians do not adhere to current recommendations for the management of childhood functional constipation, as unnecessary tests were ordered and the first-line treatment was not prescribed. Copyright © 2016. Publicado por Elsevier Editora Ltda.

  3. Pediatrician's knowledge on the approach of functional constipation

    Directory of Open Access Journals (Sweden)

    Mario C. Vieira

    Full Text Available Abstract Objective: To evaluate the pediatrician's knowledge regarding the diagnostic and therapeutic approach of childhood functional constipation. Methods: A descriptive cross-sectional study was performed with the application of a self-administered questionnaire concerning a hypothetical clinical case of childhood functional constipation with fecal incontinence to physicians (n=297 randomly interviewed at the 36th Brazilian Congress of Pediatrics in 2013. Results: The majority of the participants were females, the mean age was 44.1 years, the mean time of professional practice was 18.8 years; 56.9% were Board Certified by the Brazilian Society of Pediatrics. Additional tests were ordered by 40.4%; including abdominal radiography (19.5%, barium enema (10.4%, laboratory tests (9.8%, abdominal ultrasound (6.7%, colonoscopy (2.4%, manometry and rectal biopsy (both 1.7%. The most common interventions included lactulose (26.6%, mineral oil (17.5%, polyethylene glycol (14.5%, fiber supplement (9.1% and milk of magnesia (5.4%. Nutritional guidance (84.8%, fecal disimpaction (17.2% and toilet training (19.5% were also indicated. Conclusions: Our results show that pediatricians do not adhere to current recommendations for the management of childhood functional constipation, as unnecessary tests were ordered and the first-line treatment was not prescribed.

  4. σ-Bond Electron Delocalization in Oligosilanes as Function of Substitution Pattern, Chain Length, and Spatial Orientation

    Directory of Open Access Journals (Sweden)

    Johann Hlina

    2016-08-01

    Full Text Available Polysilanes are known to exhibit the interesting property of σ-bond electron delocalization. By employing optical spectroscopy (UV-vis, it is possible to judge the degree of delocalization and also differentiate parts of the molecules which are conjugated or not. The current study compares oligosilanes of similar chain length but different substitution pattern. The size of the substituents determines the spatial orientation of the main chain and also controls the conformational flexibility. The chemical nature of the substituents affects the orbital energies of the molecules and thus the positions of the absorption bands.

  5. Hydrogen bonded supramolecular materials

    CERN Document Server

    Li, Zhan-Ting

    2015-01-01

    This book is an up-to-date text covering topics in utilizing hydrogen bonding for constructing functional architectures and supramolecular materials. The first chapter addresses the control of photo-induced electron and energy transfer. The second chapter summarizes the formation of nano-porous materials. The following two chapters introduce self-assembled gels, many of which exhibit unique functions. Other chapters cover the advances in supramolecular liquid crystals and the versatility of hydrogen bonding in tuning/improving the properties and performance of materials. This book is designed

  6. Functional Associations by Response Overlap (FARO), a functional genomics approach matching gene expression phenotypes

    DEFF Research Database (Denmark)

    Nielsen, Henrik Bjørn; Mundy, J.; Willenbrock, Hanni

    2007-01-01

    for deriving 'Functional Association(s) by Response Overlap' (FARO) between microarray gene expression studies. The transcriptional response is defined by the set of differentially expressed genes independent from the magnitude or direction of the change. This approach overcomes the limited comparability...... to confirm and further delineate the functions of Arabidopsis MAP kinase 4 in disease and stress responses. Furthermore, we find that a large, well-defined set of genes responds in opposing directions to different stress conditions and predict the effects of different stress combinations. This demonstrates...

  7. Animal-assisted dyadic therapy: A therapy model promoting development of the reflective function in the parent-child bond.

    Science.gov (United States)

    Shani, Liat

    2017-01-01

    Animal-assisted psychotherapy (AAP) inherently incorporates standpoints, interventions, and ways of action promoting the development of the reflective function and mentalization, and thus has special value for parent-child psychotherapy. Two central tools in AAP contribute to this process. The first is the ethical stance of the therapist, who sees the animals as full partners in the therapy situation, respecting them as subjects with needs, desires, and thoughts of their own. The second tool combines nonverbal communication with animals together with the relating, in the here and now, to the understanding and decoding of body language of everyone in the setting. Nonverbal communication in AAP enables access to implicit communication patterns occurring between parent and child. This article provides a survey of theoretical development and research constituting a basis for the development of therapeutic approaches for the improvement of parent-children dynamics, followed by a description of a dyadic therapy model of a mentalization-based treatment originating from a psychoanalytic-relational orientation. Clinical examples are provided to illustrate AAP processes in parent-child psychotherapy (consent was received for examples that were not aggregated).

  8. LAMMPS Framework for Directional Dynamic Bonding

    DEFF Research Database (Denmark)

    2012-01-01

    and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework.......We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled...... to limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead...

  9. A Novel Strategy for Biomass Upgrade: Cascade Approach to the Synthesis of Useful Compounds via C-C Bond Formation Using Biomass-Derived Sugars as Carbon Nucleophiles.

    Science.gov (United States)

    Yamaguchi, Sho; Baba, Toshihide

    2016-07-20

    Due to the depletion of fossil fuels, biomass-derived sugars have attracted increasing attention in recent years as an alternative carbon source. Although significant advances have been reported in the development of catalysts for the conversion of carbohydrates into key chemicals (e.g., degradation approaches based on the dehydration of hydroxyl groups or cleavage of C-C bonds via retro-aldol reactions), only a limited range of products can be obtained through such processes. Thus, the development of a novel and efficient strategy targeted towards the preparation of a range of compounds from biomass-derived sugars is required. We herein describe the highly-selective cascade syntheses of a range of useful compounds using biomass-derived sugars as carbon nucleophiles. We focus on the upgrade of C2 and C3 oxygenates generated from glucose to yield useful compounds via C-C bond formation. The establishment of this novel synthetic methodology to generate valuable chemical products from monosaccharides and their decomposed oxygenated materials renders carbohydrates a potential alternative carbon resource to fossil fuels.

  10. Determination of the solvent density profiles across mesopores of silica-C18 bonded phases in contact with acetonitrile/water mixtures: A semi-empirical approach.

    Science.gov (United States)

    Gritti, Fabrice

    2015-09-04

    The local volume fractions of water, acetonitrile, and C18-bonded chains across the 96Åmesopores of 5μm Symmetry particles were determined semi-empirically. The semi-empirical approach was based on previous molecular dynamics studies, which provided relevant mathematical expressions for the density profiles of C18 chains and water molecules, and on minor disturbance experiments, which measured the excess amount of acetonitrile adsorbed in the pores of Symmetry-C18 particles. The pore walls of the Symmetry-C18 material were in thermodynamic equilibrium with a series of binary mixtures of water and acetonitrile. The results show that C18 chains are mostly solvated by acetonitrile molecules, water is excluded from the C18-bonded layer, and acetonitrile concentrates across a 15-25Åthick interface region between the C18 layer and the bulk phase. These actual density profiles are expected to have a direct impact on the retention behaviour of charged, polar, and neutral analytes in RPLC. They also provide clues to predict the local mobility of analytes inside the pores and a sound physico-chemical description of the phenomenon of surface diffusion observed in RPLC. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Robotic approaches for rehabilitation of hand function after stroke.

    Science.gov (United States)

    Lum, Peter S; Godfrey, Sasha B; Brokaw, Elizabeth B; Holley, Rahsaan J; Nichols, Diane

    2012-11-01

    The goal of this review was to discuss the impairments in hand function after stroke and present previous work on robot-assisted approaches to movement neurorehabilitation. Robotic devices offer a unique training environment that may enhance outcomes beyond what is possible with conventional means. Robots apply forces to the hand, allowing completion of movements while preventing inappropriate movement patterns. Evidence from the literature is emerging that certain characteristics of the human-robot interaction are preferable. In light of this evidence, the robotic hand devices that have undergone clinical testing are reviewed, highlighting the authors' work in this area. Finally, suggestions for future work are offered. The ability to deliver therapy doses far higher than what has been previously tested is a potentially key advantage of robotic devices that needs further exploration. In particular, more efforts are needed to develop highly motivating home-based devices, which can increase access to high doses of assisted movement therapy.

  12. CLARM: An integrative approach for functional modules discovery

    KAUST Repository

    Salem, Saeed M.

    2011-01-01

    Functional module discovery aims to find well-connected subnetworks which can serve as candidate protein complexes. Advances in High-throughput proteomic technologies have enabled the collection of large amount of interaction data as well as gene expression data. We propose, CLARM, a clustering algorithm that integrates gene expression profiles and protein protein interaction network for biological modules discovery. The main premise is that by enriching the interaction network by adding interactions between genes which are highly co-expressed over a wide range of biological and environmental conditions, we can improve the quality of the discovered modules. Protein protein interactions, known protein complexes, and gene expression profiles for diverse environmental conditions from the yeast Saccharomyces cerevisiae were used for evaluate the biological significance of the reported modules. Our experiments show that the CLARM approach is competitive to wellestablished module discovery methods. Copyright © 2011 ACM.

  13. Convergent approaches for defining functional imaging endophenotypes in schizophrenia

    Directory of Open Access Journals (Sweden)

    Godfrey Pearlson

    2009-11-01

    Full Text Available In complex genetic disorders such as schizophrenia, endophenotypes have potential utility both in identifying risk genes and in illuminating pathophysiology. This is due to their presumed status as closer in the etiopathological pathway to the causative genes than is the currently defining clinical phenomenology of the illness and thus their simpler genetic architecture than that of the full syndrome. There, many genes conferring slight individual risk are additive or epistatic (interactive with regard to cumulative schizophrenia risk. In addition the use of endophenotypes has encouraged a conceptual shift away from the exclusive study of categorical diagnoses in manifestly ill patients, towards the study of quantitative traits in patients, unaffected relatives and healthy controls. A more recently employed strategy is thus to study unaffected first degree relatives of schizophrenia patients, who share some of the genetic diathesis without illness-related confounds that may themselves impact fMRI task performance. Consistent with the multiple biological abnormalities associated with the disorder, many candidate endophenotypes have been advanced for schizophrenia, including measures derived from structural brain imaging, EEG, sensorimotor integration, eye movements and cognitive performance (Allen 2009, but recent data derived from quantitative functional brain imaging measures present additional attractive putative endophenotypes. We will review two major, conceptually different approaches that use fMRI in this context. One, the dominant paradigm, employs defined cognitive tasks on which schizophrenia patients perform poorly as “cognitive stress tests”. The second uses very simple probes or “task-free” approaches where performance in patients and controls is equal. We explore the potential advantages and disadvantages of each method, the associated data analytic approaches and recent studies exploring their interface with the genetic

  14. Functional Enzyme-Based Approach for Linking Microbial Community Functions with Biogeochemical Process Kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Li, Minjing [School; Qian, Wei-jun [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Gao, Yuqian [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; Shi, Liang [School; Liu, Chongxuan [Pacific Northwest National Laboratory, Richland, Washington 99354, United States; School

    2017-09-28

    The kinetics of biogeochemical processes in natural and engineered environmental systems are typically described using Monod-type or modified Monod-type models. These models rely on biomass as surrogates for functional enzymes in microbial community that catalyze biogeochemical reactions. A major challenge to apply such models is the difficulty to quantitatively measure functional biomass for constraining and validating the models. On the other hand, omics-based approaches have been increasingly used to characterize microbial community structure, functions, and metabolites. Here we proposed an enzyme-based model that can incorporate omics-data to link microbial community functions with biogeochemical process kinetics. The model treats enzymes as time-variable catalysts for biogeochemical reactions and applies biogeochemical reaction network to incorporate intermediate metabolites. The sequences of genes and proteins from metagenomes, as well as those from the UniProt database, were used for targeted enzyme quantification and to provide insights into the dynamic linkage among functional genes, enzymes, and metabolites that are necessary to be incorporated in the model. The application of the model was demonstrated using denitrification as an example by comparing model-simulated with measured functional enzymes, genes, denitrification substrates and intermediates

  15. A Model-Based Approach to Constructing Music Similarity Functions

    Directory of Open Access Journals (Sweden)

    Lamere Paul

    2007-01-01

    Full Text Available Several authors have presented systems that estimate the audio similarity of two pieces of music through the calculation of a distance metric, such as the Euclidean distance, between spectral features calculated from the audio, related to the timbre or pitch of the signal. These features can be augmented with other, temporally or rhythmically based features such as zero-crossing rates, beat histograms, or fluctuation patterns to form a more well-rounded music similarity function. It is our contention that perceptual or cultural labels, such as the genre, style, or emotion of the music, are also very important features in the perception of music. These labels help to define complex regions of similarity within the available feature spaces. We demonstrate a machine-learning-based approach to the construction of a similarity metric, which uses this contextual information to project the calculated features into an intermediate space where a music similarity function that incorporates some of the cultural information may be calculated.

  16. Network approaches to the functional analysis of microbial proteins.

    Science.gov (United States)

    Hallinan, J S; James, K; Wipat, A

    2011-01-01

    Large amounts of detailed biological data have been generated over the past few decades. Much of these data is freely available in over 1000 online databases; an enticing, but frustrating resource for microbiologists interested in a systems-level view of the structure and function of microbial cells. The frustration engendered by the need to trawl manually through hundreds of databases in order to accumulate information about a gene, protein, pathway, or organism of interest can be alleviated by the use of computational data integration to generated network views of the system of interest. Biological networks can be constructed from a single type of data, such as protein-protein binding information, or from data generated by multiple experimental approaches. In an integrated network, nodes usually represent genes or gene products, while edges represent some form of interaction between the nodes. Edges between nodes may be weighted to represent the probability that the edge exists in vivo. Networks may also be enriched with ontological annotations, facilitating both visual browsing and computational analysis via web service interfaces. In this review, we describe the construction, analysis of both single-data source and integrated networks, and their application to the inference of protein function in microbes. Copyright © 2011 Elsevier Ltd. All rights reserved.

  17. A first-prototype multi-determinant X-ray constrained wavefunction approach: the X-ray constrained extremely localized molecular orbital-valence bond method.

    Science.gov (United States)

    Genoni, Alessandro

    2017-07-01

    All the current variants of Jayatilaka's X-ray constrained wavefunction (XCW) approach work within the framework of the single-determinant wavefunction ansatz. In this paper, a first-prototype multi-determinant XCW technique is proposed. The strategy assumes that the desired XCW is written as a valence-bond-like expansion in terms of pre-determined single Slater determinants constructed with extremely localized molecular orbitals. The method, which can be particularly suitable to investigate systems with a multi-reference character, has been applied to determine the weights of the resonance structures of naphthalene at different temperatures by exploiting experimental high-resolution X-ray diffraction data. The results obtained have shown that the explicit consideration of experimental structure factors in the determination of the resonance structure weights may lead to results significantly different compared with those resulting only from the simple energy minimization.

  18. System Response Analysis and Model Order Reduction, Using Conventional Method, Bond Graph Technique and Genetic Programming

    Directory of Open Access Journals (Sweden)

    Lubna Moin

    2009-04-01

    Full Text Available This research paper basically explores and compares the different modeling and analysis techniques and than it also explores the model order reduction approach and significance. The traditional modeling and simulation techniques for dynamic systems are generally adequate for single-domain systems only, but the Bond Graph technique provides new strategies for reliable solutions of multi-domain system. They are also used for analyzing linear and non linear dynamic production system, artificial intelligence, image processing, robotics and industrial automation. This paper describes a unique technique of generating the Genetic design from the tree structured transfer function obtained from Bond Graph. This research work combines bond graphs for model representation with Genetic programming for exploring different ideas on design space tree structured transfer function result from replacing typical bond graph element with their impedance equivalent specifying impedance lows for Bond Graph multiport. This tree structured form thus obtained from Bond Graph is applied for generating the Genetic Tree. Application studies will identify key issues and importance for advancing this approach towards becoming on effective and efficient design tool for synthesizing design for Electrical system. In the first phase, the system is modeled using Bond Graph technique. Its system response and transfer function with conventional and Bond Graph method is analyzed and then a approach towards model order reduction is observed. The suggested algorithm and other known modern model order reduction techniques are applied to a 11th order high pass filter [1], with different approach. The model order reduction technique developed in this paper has least reduction errors and secondly the final model retains structural information. The system response and the stability analysis of the system transfer function taken by conventional and by Bond Graph method is compared and

  19. Robust C–C bonded porous networks with chemically designed functionalities for improved CO2 capture from flue gas

    Directory of Open Access Journals (Sweden)

    Damien Thirion

    2016-10-01

    Full Text Available Effective carbon dioxide (CO2 capture requires solid, porous sorbents with chemically and thermally stable frameworks. Herein, we report two new carbon–carbon bonded porous networks that were synthesized through metal-free Knoevenagel nitrile–aldol condensation, namely the covalent organic polymer, COP-156 and 157. COP-156, due to high specific surface area (650 m2/g and easily interchangeable nitrile groups, was modified post-synthetically into free amine- or amidoxime-containing networks. The modified COP-156-amine showed fast and increased CO2 uptake under simulated moist flue gas conditions compared to the starting network and usual industrial CO2 solvents, reaching up to 7.8 wt % uptake at 40 °C.

  20. A PBE hybrid functional study of blue-shifting and red-shifting hydrogen bonds in p hydrocarbons

    Directory of Open Access Journals (Sweden)

    Boaz Galdino de Oliveira

    2009-07-01

    Full Text Available This study examines a selected group of p hydrocarbon complexes, represented by C2H4•••HCF3, C2H2•••HCF3, C2H4•••HCF3 and C2H2•••HCF3, from a theoretical point of view. From BPBE/6-311++G(d,p calculations, the geometrical results of these complexes revealed an elongation and shortening of the H—C bond lengths of chloroform (HCCl3 and fluoroform (HCF3, respectively. In terms of the infrared spectrum, the analysis of stretch frequencies revealed that the variations in the H—C modes are essentially recognized as red and blue-shifting modes. For the purposes of understanding the two vibrational phenomena of the p hydrocarbon complexes studied here, PBE/6-311++G(d,p calculations were carried out and partitioning of atomic charges derived from the ChelpG algorithm were also used. A theoretical justification of red- and blue-shift effects was drawn up using charge-transfer analysis, which is manifested in the p bonds of acetylene and ethylene to chloroform (H—CCl3 and fluoroform (H—CF3, respectively. Finally, a further debate regarding the distinct polarizability power of chloroform and fluoroform is presented, concluding that, in comparison with fluoroform, chloroform possesses the requisite features for conventional proton donors and a red-shift is therefore observed in the C2H4•••HCCl3 and C2H2•••HCCl3 complexes.

  1. Software-aided approach to investigate peptide structure and metabolic susceptibility of amide bonds in peptide drugs based on high resolution mass spectrometry.

    Directory of Open Access Journals (Sweden)

    Tatiana Radchenko

    Full Text Available Interest in using peptide molecules as therapeutic agents due to high selectivity and efficacy is increasing within the pharmaceutical industry. However, most peptide-derived drugs cannot be administered orally because of low bioavailability and instability in the gastrointestinal tract due to protease activity. Therefore, structural modifications peptides are required to improve their stability. For this purpose, several in-silico software tools have been developed such as PeptideCutter or PoPS, which aim to predict peptide cleavage sites for different proteases. Moreover, several databases exist where this information is collected and stored from public sources such as MEROPS and ExPASy ENZYME databases. These tools can help design a peptide drug with increased stability against proteolysis, though they are limited to natural amino acids or cannot process cyclic peptides, for example. We worked to develop a new methodology to analyze peptide structure and amide bond metabolic stability based on the peptide structure (linear/cyclic, natural/unnatural amino acids. This approach used liquid chromatography / high resolution, mass spectrometry to obtain the analytical data from in vitro incubations. We collected experimental data for a set (linear/cyclic, natural/unnatural amino acids of fourteen peptide drugs and four substrate peptides incubated with different proteolytic media: trypsin, chymotrypsin, pepsin, pancreatic elastase, dipeptidyl peptidase-4 and neprilysin. Mass spectrometry data was analyzed to find metabolites and determine their structures, then all the results were stored in a chemically aware manner, which allows us to compute the peptide bond susceptibility by using a frequency analysis of the metabolic-liable bonds. In total 132 metabolites were found from the various in vitro conditions tested resulting in 77 distinct cleavage sites. The most frequent observed cleavage sites agreed with those reported in the literature. The

  2. Software-aided approach to investigate peptide structure and metabolic susceptibility of amide bonds in peptide drugs based on high resolution mass spectrometry

    Science.gov (United States)

    Fontaine, Fabien; Morettoni, Luca; Zamora, Ismael

    2017-01-01

    Interest in using peptide molecules as therapeutic agents due to high selectivity and efficacy is increasing within the pharmaceutical industry. However, most peptide-derived drugs cannot be administered orally because of low bioavailability and instability in the gastrointestinal tract due to protease activity. Therefore, structural modifications peptides are required to improve their stability. For this purpose, several in-silico software tools have been developed such as PeptideCutter or PoPS, which aim to predict peptide cleavage sites for different proteases. Moreover, several databases exist where this information is collected and stored from public sources such as MEROPS and ExPASy ENZYME databases. These tools can help design a peptide drug with increased stability against proteolysis, though they are limited to natural amino acids or cannot process cyclic peptides, for example. We worked to develop a new methodology to analyze peptide structure and amide bond metabolic stability based on the peptide structure (linear/cyclic, natural/unnatural amino acids). This approach used liquid chromatography / high resolution, mass spectrometry to obtain the analytical data from in vitro incubations. We collected experimental data for a set (linear/cyclic, natural/unnatural amino acids) of fourteen peptide drugs and four substrate peptides incubated with different proteolytic media: trypsin, chymotrypsin, pepsin, pancreatic elastase, dipeptidyl peptidase-4 and neprilysin. Mass spectrometry data was analyzed to find metabolites and determine their structures, then all the results were stored in a chemically aware manner, which allows us to compute the peptide bond susceptibility by using a frequency analysis of the metabolic-liable bonds. In total 132 metabolites were found from the various in vitro conditions tested resulting in 77 distinct cleavage sites. The most frequent observed cleavage sites agreed with those reported in the literature. The main advantages of

  3. Investigation of Drag Force on Fibres of Bonded Spherical Elements using a Coupled CFD-DEM Approach

    DEFF Research Database (Denmark)

    Jensen, Anna Lyhne; Sørensen, Henrik; Rosendahl, Lasse Aistrup

    2016-01-01

    Clogging in wastewater pumps is often caused by flexible, stringy objects. Therefore, simulation of clogging effects in wastewater pumps entails simulation of such flexible objects and the interaction between these objects and fluid in the pump. Using a coupled CFD-DEM approach, the flexible obje...

  4. Evaluation of hydrogen bond networks in cellulose Iβ and II crystals using density functional theory and Car-Parrinello molecular dynamics.

    Science.gov (United States)

    Hayakawa, Daichi; Nishiyama, Yoshiharu; Mazeau, Karim; Ueda, Kazuyoshi

    2017-09-08

    Crystal models of cellulose Iβ and II, which contain various hydrogen bonding (HB) networks, were analyzed using density functional theory and Car-Parrinello molecular dynamics (CPMD) simulations. From the CPMD trajectories, the power spectra of the velocity correlation functions of hydroxyl groups involved in hydrogen bonds were calculated. For the Iβ allomorph, HB network A, which is dominant according to the neutron diffraction data, was stable, and the power spectrum represented the essential features of the experimental IR spectra. In contrast, network B, which is a minor structure, was unstable because its hydroxymethyl groups reoriented during the CPMD simulation, yielding a different crystal structure to that determined by experiments. For the II allomorph, a HB network A is proposed based on diffraction data, whereas molecular modeling identifies an alternative network B. Our simulations showed that the interaction energies of the cellulose II (B) model are slightly more favorable than model II(A). However, the evaluation of the free energy should be waited for the accurate determination from the energy point of view. For the IR calculation, cellulose II (B) model reproduces the spectra better than model II (A). Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Predicting Bond Betas using Macro-Finance Variables

    OpenAIRE

    Aslanidis, Nektarios; Christiansen, Charlotte; Cipollini, Andrea

    2017-01-01

    We conduct in-sample and out-of-sample forecasting using the new approach of combining explanatory variables through complete subset regressions (CSR). We predict bond CAPM betas and bond returns conditioning on various macro-fi…nance variables. We explore differences across long-term government bonds, investment grade corporate bonds, and high-yield corporate bonds. The CSR method performs well in predicting bond betas, especially in-sample, and, mainly high-yield bond betas when the focus i...

  6. HOW DO DIFFERENT INTERNET USE FUNCTIONS AFFECT BRIDGING AND BONDING SOCIAL CAPITAL? AN EMPIRICAL STUDY OF THE CHINESE INTERNATIONAL STUDENTS IN JAPAN

    Directory of Open Access Journals (Sweden)

    Yu Guo

    2014-06-01

    Full Text Available This study examines the relationship between Internet use and social capital in an intercultural context and investigates how different Internet use functions are related to social capital. Data were collected from the survey among 155 Chinese international students studying in Japan’s universities. The results showed that Internet use intensity negatively influenced individuals’ bonding social capital. It was also found that the use of the Internet for staying informed would have positive effects on bridging social capital. However, no significant relationship was found between using the Internet for interacting with others and the two types of social capital. These findings fill the gaps in existing studies on Internet effectiveness and help to provide knowledge about the influences of various Internet use functions on establishing and maintaining social ties.

  7. Functional implications of the proximal site hydrogen bonding network in Vitreoscilla hemoglobin (VHb): role of Tyr95 (G5) and Tyr126 (H12).

    Science.gov (United States)

    Kaur, Ramandeep; Ahuja, Sandhya; Anand, Arvind; Singh, Balwinder; Stark, Benjamin C; Webster, Dale A; Dikshit, Kanak L

    2008-10-15

    Although Vitreoscilla hemoglobin (VHb) carries a conventional globin fold, its proximal site geometry is unique in having a hydrogen-bonding network between proximal site residues, HisF8-TyrG5-GluH23 and TyrG5-TyrH12. TyrG5 and TyrH12 were mutated to study their relevance in VHb function. VHb G5 mutants (Tyr95Phe and Tyr95Leu showed no stable oxyform and nitric oxide dioxygenase activity, whereas, VHb H12 mutants (Tyr126Phe and Tyr126Leu) displayed little change in their oxygen affinity indicating a crucial role of Tyr95 in protein function. The VHb H12 mutant, Tyr126Leu, enhanced the intracellular pool of oxygen and cell growth better than VHb. Molecular modeling suggests that the replacement of tyrosine with leucine in Tyr126Leu creates an opening on the protein surface that may facilitate oxygen diffusion and accumulation.

  8. Nature of the bonding in the AuNgX (Ng = Ar, Kr, Xe; X = F, Cl, Br, I) molecules. Topological study on electron density and the electron localization function (ELF).

    Science.gov (United States)

    Makarewicz, Emilia; Gordon, Agnieszka J; Berski, Slawomir

    2015-03-19

    Topological analysis of the electron localization function (ELF) has been carried out for the AuNgX (Ng = Ar, Kr, Xe; X = F, Cl, Br, I) molecules using the wave function approximated by the CCSD, MP2, and DFT(B3LYP, M062X) methods including zero-order regular approximation (ZORA). In the Ng-F bond, the bonding disynaptic attractor V(Ng,F) is missing; therefore, there are no signs of the covalent binding. The nature of the Au-Ng bond depends on the computational method used. Analysis of the ELF carried out for the AuArF and AuXeF molecules, with the wave function approximated by the CCSD and MP2 methods, shows the V(Au,Ng) attractor possibly corresponding to a partially covalent binding between the gold and noble gas atom. However, its very small basin population (<1e) and a very large value of the variance of the basin population suggest that the Au-Ng bond has a very delocalized character. Such bond nature may be related to the charge shift concept with a resonance of the Au(-+)NgX, Au(+-)NgX hybrids. The weakest Au-Ng bond, in terms of the smallest amount of electron density for the V(Au,Ng) basin, is found for the AuKrF molecule with the CCSD method (0.13e). The MP2 method, however, does not yield any V(Au, Ng) population; hence, the covalent Au-Kr bond is not confirmed. Because the V(Au,Ng) attractor is also not observed with the DFT method, the proper characterization of the Au-Ng bond requires proper description of correlation effects. Additional studies on the Au2 and [AuXe](+) molecules, performed at the CCSD and B3LYP levels, exhibit no V(Au,Au) and V(Au,Xe) bonding basins either.

  9. Chebyshev matrix product state approach for spectral functions

    Science.gov (United States)

    Holzner, Andreas; Weichselbaum, Andreas; McCulloch, Ian P.; Schollwöck, Ulrich; von Delft, Jan

    2011-05-01

    We show that recursively generated Chebyshev expansions offer numerically efficient representations for calculating zero-temperature spectral functions of one-dimensional lattice models using matrix product state (MPS) methods. The main features of this Chebyshev matrix product state (CheMPS) approach are as follows: (i) it achieves uniform resolution over the spectral function’s entire spectral width; (ii) it can exploit the fact that the latter can be much smaller than the model’s many-body bandwidth; (iii) it offers a well-controlled broadening scheme that allows finite-size effects to be either resolved or smeared out, as desired; (iv) it is based on using MPS tools to recursively calculate a succession of Chebyshev vectors |tn>, (v) the entanglement entropies of which were found to remain bounded with increasing recursion order n for all cases analyzed here; and (vi) it distributes the total entanglement entropy that accumulates with increasing n over the set of Chebyshev vectors |tn>, which need not be combined into a single vector. In this way, the growth in entanglement entropy that usually limits density matrix renormalization group (DMRG) approaches is packaged into conveniently manageable units. We present zero-temperature CheMPS results for the structure factor of spin-(1)/(2) antiferromagnetic Heisenberg chains and perform a detailed finite-size analysis. Making comparisons to three benchmark methods, we find that CheMPS (a) yields results comparable in quality to those of correction-vector DMRG, at dramatically reduced numerical cost; (b) agrees well with Bethe ansatz results for an infinite system, within the limitations expected for numerics on finite systems; and (c) can also be applied in the time domain, where it has potential to serve as a viable alternative to time-dependent DMRG (in particular, at finite temperatures). Finally, we present a detailed error analysis of CheMPS for the case of the noninteracting resonant level model.

  10. Bond-based 2D TOMOCOMD-CARDD approach for drug discovery: aiding decision-making in `in silico' selection of new lead tyrosinase inhibitors

    Science.gov (United States)

    Marrero-Ponce, Yovani; Khan, Mahmud Tareq Hassan; Casañola-Martín, Gerardo M.; Ather, Arjumand; Sultankhodzhaev, Mukhlis N.; García-Domenech, Ramón; Torrens, Francisco; Rotondo, Richard

    2007-04-01

    In this paper, we present a new set of bond-level TOMOCOMD-CARDD molecular descriptors (MDs), the bond-based bilinear indices, based on a bilinear map similar to those defined in linear algebra. These novel MDs are used here in Quantitative Structure-Activity Relationship (QSAR) studies of tyrosinase inhibitors, for finding functions that discriminate between the tyrosinase inhibitor compounds and inactive ones. In total 14 models were obtained and the best two discriminant functions (Eqs. 32 and 33) shown globally good classification of 91.00% and 90.17%, respectively, in the training set. The test set had accuracies of 93.33% and 88.89% for the models 32 and 33, correspondingly. A simulated virtual screening was also carried out to prove the quality of the determined models. In a final step, the fitted models were used in the biosilico identification of new synthesized tetraketones, where a good agreement could be observed between the theoretical and experimental results. Four compounds of the novel bioactive chemicals discovered as tyrosinase inhibitors: TK10 (IC50 = 2.09 μM), TK11 (IC50 = 2.61 μM), TK21 (IC50 = 2.06 μM), TK23 (IC50 = 3.19 μM), showed more potent activity than l-mimose (IC50 = 3.68 μM). Besides, for this study a heterogeneous database of tyrosinase inhibitors was collected, and could be a useful tool for the scientist in the domain of tyrosinase enzyme researches. The current report could help to shed some clues in the identification of new chemicals that inhibits enzyme tyrosinase, for entering in the pipeline of drug discovery development.

  11. A comparison of approaches to estimate the resonance energy

    NARCIS (Netherlands)

    Zielinski, Marcin; Havenith, Remco W. A.; Jenneskens, Leonardus W.; van Lenthe, Joop H.

    We discuss Ab Initio approaches to calculate the energy lowering (stabilisation) due to aromaticity. We compare the valence bond method and the block-localised wave function approaches to calculate the resonance energy. We conclude that the valence bond approach employs a Pauling-Wheland resonance

  12. The neurobiology of pair bond formation, bond disruption, and social buffering.

    Science.gov (United States)

    Lieberwirth, Claudia; Wang, Zuoxin

    2016-10-01

    Enduring social bonds play an essential role in human society. These bonds positively affect psychological, physiological, and behavioral functions. Here, we review the recent literature on the neurobiology, particularly the role of oxytocin and dopamine, of pair bond formation, bond disruption, and social buffering effects on stress responses, from studies utilizing the socially monogamous prairie vole (Microtus ochrogaster). Published by Elsevier Ltd.

  13. Executive Function and Food Approach Behavior in Middle Childhood

    Directory of Open Access Journals (Sweden)

    Karoline eGroppe

    2014-05-01

    Full Text Available Executive function (EF has long been considered to be a unitary, domain-general cognitive ability. However, recent research suggests differentiating ‘hot’ affective and ‘cool’ cognitive aspects of EF. Yet, findings regarding this two-factor construct are still inconsistent. In particular, the development of this factor structure remains unclear and data on school-aged children is lacking. Furthermore, studies linking EF and overweight or obesity suggest that EF contributes to the regulation of eating behavior. So far, however, the links between EF and eating behavior have rarely been investigated in children and non-clinical populations.First, we examined whether EF can be divided into hot and cool factors or whether they actually correspond to a unitary construct in middle childhood. Second, we examined how hot and cool EF are associated with different eating styles that put children at risk of becoming overweight during development. Hot and cool EF were assessed experimentally in a non-clinical population of 1,657 elementary-school children (aged 6-11 years. The ‘food approach’ behavior was rated mainly via parent questionnaires.Findings indicate that hot EF is distinguishable from cool EF. However, only cool EF seems to represent a coherent functional entity, whereas hot EF does not seem to be a homogenous construct. This was true for a younger and an older subgroup of children. Furthermore, different EF components were correlated with eating styles, such as responsiveness to food, desire to drink, and restrained eating in girls but not in boys. This shows that lower levels of EF are not only seen in clinical populations of obese patients but are already associated with food approach styles in a normal population of elementary school-aged girls. Although the direction of effect still has to be clarified, results point to the possibility that EF constitutes a risk factor for eating styles contributing to the development of

  14. Selectionist and evolutionary approaches to brain function: a critical appraisal

    Directory of Open Access Journals (Sweden)

    Chrisantha Thomas Fernando

    2012-04-01

    Full Text Available We consider approaches to brain dynamics and function that have been claimed to be Darwinian. These include Edelman’s theory of neuronal group selection, Changeux’s theory of synaptic selection and selective stabilization of pre-representations, Seung’s Darwinian synapse, Loewenstein’s synaptic melioration, Adam’s selfish synapse and Calvin’s replicating activity patterns. Except for the last two, the proposed mechanisms are selectionist but not truly Darwinian, because no replicators with information transfer to copies and hereditary variation can be identified in them. All of them fit, however, a generalized selectionist framework conforming to the picture of Price’s covariance formulation, which deliberately was not specific even to selection in biology, and therefore does not imply an algorithmic picture of biological evolution. Bayesian models and reinforcement learning are formally in agreement with selection dynamics. A classification of search algorithms is shown to include Darwinian replicators (evolutionary units with multiplication, heredity and variability as the most powerful mechanism in a sparsely occupied search space. Examples of why parallel competitive search with information transfer among the units is efficient are given. Finally, we review our recent attempts to construct and analyze simple models of true Darwinian evolutionary units in the brain in terms of connectivity and activity copying of neuronal groups. Although none of the proposed neuronal replicators include miraculous mechanisms, their identification remains a challenge but also a great promise.

  15. Harnessing systems biology approaches to engineer functional microvascular networks.

    Science.gov (United States)

    Sefcik, Lauren S; Wilson, Jennifer L; Papin, Jason A; Botchwey, Edward A

    2010-06-01

    Microvascular remodeling is a complex process that includes many cell types and molecular signals. Despite a continued growth in the understanding of signaling pathways involved in the formation and maturation of new blood vessels, approximately half of all compounds entering clinical trials will fail, resulting in the loss of much time, money, and resources. Most pro-angiogenic clinical trials to date have focused on increasing neovascularization via the delivery of a single growth factor or gene. Alternatively, a focus on the concerted regulation of whole networks of genes may lead to greater insight into the underlying physiology since the coordinated response is greater than the sum of its parts. Systems biology offers a comprehensive network view of the processes of angiogenesis and arteriogenesis that might enable the prediction of drug targets and whether or not activation of the targets elicits the desired outcome. Systems biology integrates complex biological data from a variety of experimental sources (-omics) and analyzes how the interactions of the system components can give rise to the function and behavior of that system. This review focuses on how systems biology approaches have been applied to microvascular growth and remodeling, and how network analysis tools can be utilized to aid novel pro-angiogenic drug discovery.

  16. Remodeling Functional Connectivity in Multiple Sclerosis: A Challenging Therapeutic Approach

    Directory of Open Access Journals (Sweden)

    Mario Stampanoni Bassi

    2017-12-01

    Full Text Available Neurons in the central nervous system are organized in functional units interconnected to form complex networks. Acute and chronic brain damage disrupts brain connectivity producing neurological signs and/or symptoms. In several neurological diseases, particularly in Multiple Sclerosis (MS, structural imaging studies cannot always demonstrate a clear association between lesion site and clinical disability, originating the “clinico-radiological paradox.” The discrepancy between structural damage and disability can be explained by a complex network perspective. Both brain networks architecture and synaptic plasticity may play important roles in modulating brain networks efficiency after brain damage. In particular, long-term potentiation (LTP may occur in surviving neurons to compensate network disconnection. In MS, inflammatory cytokines dramatically interfere with synaptic transmission and plasticity. Importantly, in addition to acute and chronic structural damage, inflammation could contribute to reduce brain networks efficiency in MS leading to worse clinical recovery after a relapse and worse disease progression. These evidence suggest that removing inflammation should represent the main therapeutic target in MS; moreover, as synaptic plasticity is particularly altered by inflammation, specific strategies aimed at promoting LTP mechanisms could be effective for enhancing clinical recovery. Modulation of plasticity with different non-invasive brain stimulation (NIBS techniques has been used to promote recovery of MS symptoms. Better knowledge of features inducing brain disconnection in MS is crucial to design specific strategies to promote recovery and use NIBS with an increasingly tailored approach.

  17. Diffusion bonding

    International Nuclear Information System (INIS)

    Anderson, R.C.

    1976-01-01

    A method is described for joining beryllium to beryllium by diffusion bonding. At least one surface portion of at least two beryllium pieces is coated with nickel. A coated surface portion is positioned in a contiguous relationship with another surface portion and subjected to an environment having an atmosphere at a pressure lower than ambient pressure. A force is applied on the beryllium pieces for causing the contiguous surface portions to abut against each other. The contiguous surface portions are heated to a maximum temperature less than the melting temperature of the beryllium, and the applied force is decreased while increasing the temperature after attaining a temperature substantially above room temperature. A portion of the applied force is maintained at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions

  18. Weighted density approximation for bonding in molecules: ring and cage polymers

    CERN Document Server

    Sweatman, M B

    2003-01-01

    The focus of this work is the bonded contribution to the intrinsic Helmholtz free energy of molecules. A weighted density approximation (WDA) for this contribution is presented within the interaction site model (ISM) for ring and cage polymers. The resulting density functional theory (ISM/WDA) for these systems is no more complex than theories for a pure simple fluid, and much less complex than density functional approaches that treat the bonding functional exactly. The ISM/WDA bonding functional is much more accurate than either the ISM/HNC or ISM/PY bonding functionals, which are related to the reference interaction-site model (RISM)/HNC and RISM/PY integral equations respectively, for ideal ring polymers. This means that the ISM/WDA functional should generally be more accurate for most 'real' ring or cage polymer systems when any reasonable approximation for the 'excess' contribution to the intrinsic Helmholtz free energy is employed.

  19. Weighted density approximation for bonding in molecules: ring and cage polymers

    International Nuclear Information System (INIS)

    Sweatman, M B

    2003-01-01

    The focus of this work is the bonded contribution to the intrinsic Helmholtz free energy of molecules. A weighted density approximation (WDA) for this contribution is presented within the interaction site model (ISM) for ring and cage polymers. The resulting density functional theory (ISM/WDA) for these systems is no more complex than theories for a pure simple fluid, and much less complex than density functional approaches that treat the bonding functional exactly. The ISM/WDA bonding functional is much more accurate than either the ISM/HNC or ISM/PY bonding functionals, which are related to the reference interaction-site model (RISM)/HNC and RISM/PY integral equations respectively, for ideal ring polymers. This means that the ISM/WDA functional should generally be more accurate for most 'real' ring or cage polymer systems when any reasonable approximation for the 'excess' contribution to the intrinsic Helmholtz free energy is employed

  20. A desirability functions-based approach for simultaneous ...

    African Journals Online (AJOL)

    In order to improve product quality, all these quantitative and qualitative responses must be optimized simultaneously. ... Few researchers have proposed some alternative approaches for optimizing an ... quantitative and ordinal response variables simultaneously under Taguchi's framework of robust design approach.

  1. FINAL TECHNICAL REPORT for grant DE-FG02-93ER14353 "Carbon-Hydrogen Bond Functionalization Catalyzed by Transition Metal Systems"

    Energy Technology Data Exchange (ETDEWEB)

    Goldman, Alan S

    2012-05-21

    Alkanes are our most abundant organic resource but are highly resistant to selective chemical transformations. Alkenes (olefins) by contrast are the single most versatile class of molecules for selective transformations, and are intermediates in virtually every petrochemical process as well as a vast range of commodity and fine chemical processes. Over the course of this project we have developed the most efficient catalysts to date for the selective conversion of alkanes to give olefins, and have applied these catalysts to other dehydrogenation reactions. We have also developed some of the first efficient catalysts for carbonylation of alkanes and arenes to give aldehydes. The development of these catalysts has been accompanied by elucidation of the mechanism of their operation and the factors controlling the kinetics and thermodynamics of C-H bond activation and other individual steps of the catalytic cycles. This fundamental understanding will allow the further improvement of these catalysts, as well as the development of the next generation of catalysts for the functionalization of alkanes and other molecules containing C-H bonds.

  2. Amino-Functionalized Multiwalled Carbon Nanotubes Lead to Successful Ring-Opening Polymerization of Poly(ε-caprolactone): Enhanced Interfacial Bonding and Optimized Mechanical Properties.

    Science.gov (United States)

    Roumeli, Eleftheria; Papageorgiou, Dimitrios G; Tsanaktsis, Vasilios; Terzopoulou, Zoe; Chrissafis, Konstantinos; Avgeropoulos, Apostolos; Bikiaris, Dimitrios N

    2015-06-03

    In this work, the synthesis, structural characteristics, interfacial bonding, and mechanical properties of poly(ε-caprolactone) (PCL) nanocomposites with small amounts (0.5, 1.0, and 2.5 wt %) of amino-functionalized multiwalled carbon nanotubes (f-MWCNTs) prepared by ring-opening polymerization (ROP) are reported. This method allows the creation of a covalent-bonding zone on the surface of nanotubes, which leads to efficient debundling and therefore satisfactory dispersion and effective load transfer in the nanocomposites. The high covalent grafting extent combined with the higher crystallinity provide the basis for a significant enhancement of the mechanical properties, which was detected in the composites with up to 1 wt % f-MWCNTs. Increasing filler concentration encourages intrinsic aggregation forces, which allow only minor grafting efficiency and poorer dispersion and hence inferior mechanical performance. f-MWCNTs also cause a significant improvement on the polymerization reaction of PCL. Indeed, the in situ polymerization kinetics studies reveal a significant decrease in the reaction temperature, by a factor of 30-40 °C, combined with accelerated the reaction kinetics during initiation and propagation and a drastically reduced effective activation energy.

  3. Reconstructing Regional Ionospheric Electron Density: A Combined Spherical Slepian Function and Empirical Orthogonal Function Approach

    Science.gov (United States)

    Farzaneh, Saeed; Forootan, Ehsan

    2018-03-01

    The computerized ionospheric tomography is a method for imaging the Earth's ionosphere using a sounding technique and computing the slant total electron content (STEC) values from data of the global positioning system (GPS). The most common approach for ionospheric tomography is the voxel-based model, in which (1) the ionosphere is divided into voxels, (2) the STEC is then measured along (many) satellite signal paths, and finally (3) an inversion procedure is applied to reconstruct the electron density distribution of the ionosphere. In this study, a computationally efficient approach is introduced, which improves the inversion procedure of step 3. Our proposed method combines the empirical orthogonal function and the spherical Slepian base functions to describe the vertical and horizontal distribution of electron density, respectively. Thus, it can be applied on regional and global case studies. Numerical application is demonstrated using the ground-based GPS data over South America. Our results are validated against ionospheric tomography obtained from the constellation observing system for meteorology, ionosphere, and climate (COSMIC) observations and the global ionosphere map estimated by international centers, as well as by comparison with STEC derived from independent GPS stations. Using the proposed approach, we find that while using 30 GPS measurements in South America, one can achieve comparable accuracy with those from COSMIC data within the reported accuracy (1 × 1011 el/cm3) of the product. Comparisons with real observations of two GPS stations indicate an absolute difference is less than 2 TECU (where 1 total electron content unit, TECU, is 1016 electrons/m2).

  4. Cooperativity in Surface Bonding and Hydrogen Bonding of Water and Hydroxyl at Metal Surfaces

    DEFF Research Database (Denmark)

    Schiros, T.; Ogasawara, H.; Naslund, L. A.

    2010-01-01

    of the mixed phase at metal surfaces. The surface bonding can be considered to be similar to accepting a hydrogen bond, and we can thereby apply general cooperativity rules developed for hydrogen-bonded systems. This provides a simple understanding of why water molecules become more strongly bonded...... to the surface upon hydrogen bonding to OH and why the OH surface bonding is instead weakened through hydrogen bonding to water. We extend the application of this simple model to other observed cooperativity effects for pure water adsorption systems and H3O+ on metal surfaces.......We examine the balance of surface bonding and hydrogen bonding in the mixed OH + H2O overlayer on Pt(111), Cu(111), and Cu(110) via density functional theory calculations. We find that there is a cooperativity effect between surface bonding and hydrogen bonding that underlies the stability...

  5. Electronic Coupling Calculations for Bridge-Mediated Charge Transfer Using Constrained Density Functional Theory (CDFT) and Effective Hamiltonian Approaches at the Density Functional Theory (DFT) and Fragment-Orbital Density Functional Tight Binding (FODFTB) Level.

    Science.gov (United States)

    Gillet, Natacha; Berstis, Laura; Wu, Xiaojing; Gajdos, Fruzsina; Heck, Alexander; de la Lande, Aurélien; Blumberger, Jochen; Elstner, Marcus

    2016-10-11

    In this article, four methods to calculate charge transfer integrals in the context of bridge-mediated electron transfer are tested. These methods are based on density functional theory (DFT). We consider two perturbative Green's function effective Hamiltonian methods (first, at the DFT level of theory, using localized molecular orbitals; second, applying a tight-binding DFT approach, using fragment orbitals) and two constrained DFT implementations with either plane-wave or local basis sets. To assess the performance of the methods for through-bond (TB)-dominated or through-space (TS)-dominated transfer, different sets of molecules are considered. For through-bond electron transfer (ET), several molecules that were originally synthesized by Paddon-Row and co-workers for the deduction of electronic coupling values from photoemission and electron transmission spectroscopies, are analyzed. The tested methodologies prove to be successful in reproducing experimental data, the exponential distance decay constant and the superbridge effects arising from interference among ET pathways. For through-space ET, dedicated π-stacked systems with heterocyclopentadiene molecules were created and analyzed on the basis of electronic coupling dependence on donor-acceptor distance, structure of the bridge, and ET barrier height. The inexpensive fragment-orbital density functional tight binding (FODFTB) method gives similar results to constrained density functional theory (CDFT) and both reproduce the expected exponential decay of the coupling with donor-acceptor distances and the number of bridging units. These four approaches appear to give reliable results for both TB and TS ET and present a good alternative to expensive ab initio methodologies for large systems involving long-range charge transfers.

  6. A Gendered Approach to Understanding the Roles of Social Bonding, Personal Control, and Strain on College Dating Violence in Emerging Adulthood

    OpenAIRE

    Paat, Yok-Fong; Markham, Christine

    2016-01-01

    Borrowing insights from concepts that have been shown to predict deviant or criminal outcomes (i.e., social bonding, personal control, and strain), this study examined dating violence from the perpetrators’ and gender-relevance perspective among young college students (18–25 years old). This study raised 2 research questions: Were social bonding, personal control, and strain associated with college dating violence? How did these associations differ by gender? In sum, 2 types of social bonding...

  7. Rhodium-catalyzed C-H bond activation for the synthesis of quinonoid compounds: Significant Anti-Trypanosoma cruzi activities and electrochemical studies of functionalized quinones.

    Science.gov (United States)

    Jardim, Guilherme A M; Silva, Thaissa L; Goulart, Marilia O F; de Simone, Carlos A; Barbosa, Juliana M C; Salomão, Kelly; de Castro, Solange L; Bower, John F; da Silva Júnior, Eufrânio N

    2017-08-18

    Thirty four halogen and selenium-containing quinones, synthesized by rhodium-catalyzed C-H bond activation and palladium-catalyzed cross-coupling reactions, were evaluated against bloodstream trypomastigotes of T. cruzi. We have identified fifteen compounds with IC 50 /24 h values of less than 2 μM. Electrochemical studies on A-ring functionalized naphthoquinones were also performed aiming to correlate redox properties with trypanocidal activity. For instance, (E)-5-styryl-1,4-naphthoquinone 59 and 5,8-diiodo-1,4-naphthoquinone 3, which are around fifty fold more active than the standard drug benznidazole, are potential derivatives for further investigation. These compounds represent powerful new agents useful in Chagas disease therapy. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  8. Tantalum surface oxidation: Bond relaxation, energy entrapment, and electron polarization

    Energy Technology Data Exchange (ETDEWEB)

    Guo, Yongling [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Bo, Maolin [Yangtze Normal University, College of Mechanical and Electrical Engineering, Chongqing 408100 (China); Wang, Yan [School of Information and Electronic Engineering, Hunan University of Science and Technology, Hunan 411201 (China); Liu, Yonghui [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China); Sun, Chang Q. [NOVITAS, School of Electrical and Electronic Engineering, Nanyang Technological University, Singapore 639798 (Singapore); Huang, Yongli, E-mail: huangyongli@xtu.edu.cn [Key Laboratory of Low-Dimensional Materials and Application Technologies (Ministry of Education), Hunan Provincial Key Laboratory of Thin Film Materials and Devices, Faculty of Materials Science and Engineering, Xiangtan University, Hunan 411105 (China)

    2017-02-28

    Graphical abstract: The bond, electron and energy relaxation result in core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Highlights: • Increasing the oxygen coverage lowers the adsorption energy associated with lattice reconstruction. • Electrons transfer from Ta surface atoms to sp-hydrated oxygen, creating dipole moment that decreases the work function. • Oxygen chemisorption modified valence density-of-state (DOS) for Ta with four excessive DOS features: O−Ta bonding, O{sup 2−} lone pairs, Ta+ electron holes, and the lone-pair polarized Ta dipoles. • The bond, electron and energy relaxation between surface undercoordinated atoms are responsible for core level energy shift, local densification, quantum entrapment and electron polarization of bonding electrons. - Abstract: A combination of photoelectron spectrometric analysis and density functional theory calculations has enabled reconciliation of the bond-energy-electron relaxation for the Ta(100, 110, 111) surfaces chemisorbed with oxygen at different coverages. Results show that increasing oxygen coverage lowers the adsorption energy associated with lattice reconstruction. Valence electrons transfer from Ta surface atoms to oxygen to create four excessive DOS features in terms of O−Ta bonding, lone pairs of oxygen, Ta{sup +} electron holes, and polarized Ta dipoles. Oxidation proceeds in the following dynamics: oxygen gets electrons from two neighboring Ta atoms left behind Ta{sup +}; the sp{sup 3}-orbital hybridization takes place with additional two electron lone pairs, the lone pairs polarize the other two Ta neighbors becoming dipoles. X-ray photoelectron spectral analysis results in the 4f binding energy of an isolated Ta atom and its shift upon bond formation and oxidation. Exercises provide not only a promising numerical approach for the quantitative information about the bond and electronic behavior but also consistent

  9. A Geometric Approach to Visualization of Variability in Functional Data

    KAUST Repository

    Xie, Weiyi

    2016-12-19

    We propose a new method for the construction and visualization of boxplot-type displays for functional data. We use a recent functional data analysis framework, based on a representation of functions called square-root slope functions, to decompose observed variation in functional data into three main components: amplitude, phase, and vertical translation. We then construct separate displays for each component, using the geometry and metric of each representation space, based on a novel definition of the median, the two quartiles, and extreme observations. The outlyingness of functional data is a very complex concept. Thus, we propose to identify outliers based on any of the three main components after decomposition. We provide a variety of visualization tools for the proposed boxplot-type displays including surface plots. We evaluate the proposed method using extensive simulations and then focus our attention on three real data applications including exploratory data analysis of sea surface temperature functions, electrocardiogram functions and growth curves.

  10. Unsymmetrical Chelation of N-Thioether-Functionalized Bis(diphenylphosphino)amine-Type Ligands and Substituent Effects on the Nuclearity of Iron(II) Complexes: Structures, Magnetism, and Bonding.

    Science.gov (United States)

    Fliedel, Christophe; Rosa, Vitor; Falceto, Andrés; Rosa, Patrick; Alvarez, Santiago; Braunstein, Pierre

    2015-07-06

    Starting from the short-bite ligands N-thioether-functionalized bis(diphenylphosphino)amine-type (Ph2P)2N(CH2)3SMe (1) and (Ph2P)2N(p-C6H4)SMe (2), the Fe(II) complexes [FeCl2(1)]n (3), [FeCl2(2)]2 (4), [Fe(OAc)(1)2]PF6 (5), and [Fe(OAc)(2)2]PF6 (6) were synthesized and characterized by Fourier transform IR, mass spectrometry, elemental analysis, and also by X-ray diffraction for 3, 4, and 6. Complex 3 is a coordination polymer in which 1 acts as a P,P-pseudochelate and a (P,P),S-bridge, whereas 4 has a chlorido-bridged dinuclear structure in which 2 acts only as a P,P-pseudochelate. Since these complexes were obtained under strictly similar synthetic and crystallization conditions, these unexpected differences were ascribed to the different spacer between the nitrogen atom and the −SMe group. In both compounds, one Fe–P bond was found to be unusually long, and a theoretical analysis was performed to unravel the electronic or steric reasons for this difference. Density functional theory calculations were performed for a set of complexes of general formula [FeCl2(SR2){R21PN(R2)P′R23}] (R = H, Me; R1, R2, and R3 = H, Me, Ph), to understand the reasons for the significant deviation of the iron coordination sphere away from tetrahedral as well as from trigonal bipyramidal and the varying degree of unsymmetry of the two Fe–P bonds involving pseudochelating PN(R)P ligands. Electronic factors nicely explain the observed structures, and steric reasons were further ruled out by the structural analysis in the solid-state of the bis-chelated complex 6, which displays usual and equivalent Fe–P bond lengths. Magnetic susceptibility studies were performed to examine how the structural differences between 3 and 4 would affect the interactions between the iron centers, and it was concluded that 3 behaves as an isolated high-spin Fe(II) mononuclear complex, while significant intra- and intermolecular ferromagnetic interactions were evidenced for 4 at low temperatures

  11. Bond graph modeling of centrifugal compression systems

    OpenAIRE

    Uddin, Nur; Gravdahl, Jan Tommy

    2015-01-01

    A novel approach to model unsteady fluid dynamics in a compressor network by using a bond graph is presented. The model is intended in particular for compressor control system development. First, we develop a bond graph model of a single compression system. Bond graph modeling offers a different perspective to previous work by modeling the compression system based on energy flow instead of fluid dynamics. Analyzing the bond graph model explains the energy flow during compressor surge. Two pri...

  12. A desirability functions-based approach for simultaneous ...

    African Journals Online (AJOL)

    simultaneous optimization of quantitative and ordinal response variables. But none of these approaches results in an efficient optimal solution with respect to the desirability values of all the individual response variables. It motivated us to develop a more useful approach for simultaneously optimizing industrial processes ...

  13. A statistical mechanical theory of proton transport kinetics in hydrogen-bonded networks based on population correlation functions with applications to acids and bases.

    Science.gov (United States)

    Tuckerman, Mark E; Chandra, Amalendu; Marx, Dominik

    2010-09-28

    Extraction of relaxation times, lifetimes, and rates associated with the transport of topological charge defects in hydrogen-bonded networks from molecular dynamics simulations is a challenge because proton transfer reactions continually change the identity of the defect core. In this paper, we present a statistical mechanical theory that allows these quantities to be computed in an unbiased manner. The theory employs a set of suitably defined indicator or population functions for locating a defect structure and their associated correlation functions. These functions are then used to develop a chemical master equation framework from which the rates and lifetimes can be determined. Furthermore, we develop an integral equation formalism for connecting various types of population correlation functions and derive an iterative solution to the equation, which is given a graphical interpretation. The chemical master equation framework is applied to the problems of both hydronium and hydroxide transport in bulk water. For each case it is shown that the theory establishes direct links between the defect's dominant solvation structures, the kinetics of charge transfer, and the mechanism of structural diffusion. A detailed analysis is presented for aqueous hydroxide, examining both reorientational time scales and relaxation of the rotational anisotropy, which is correlated with recent experimental results for these quantities. Finally, for OH(-)(aq) it is demonstrated that the "dynamical hypercoordination mechanism" is consistent with available experimental data while other mechanistic proposals are shown to fail. As a means of going beyond the linear rate theory valid from short up to intermediate time scales, a fractional kinetic model is introduced in the Appendix in order to describe the nonexponential long-time behavior of time-correlation functions. Within the mathematical framework of fractional calculus the power law decay ∼t(-σ), where σ is a parameter of the

  14. Effects of Bonding Types and Functional Groups on CO 2 Capture using Novel Multiphase Systems of Liquid-like Nanoparticle Organic Hybrid Materials

    KAUST Repository

    Lin, Kun-Yi Andrew

    2011-08-01

    Novel liquid-like nanoparticle organic hybrid materials (NOHMs) which possess unique features including negligible vapor pressure and a high degree of tunability were synthesized and their physical and chemical properties as well as CO 2 capture capacities were investigated. NOHMs can be classified based on the synthesis methods involving different bonding types, the existence of linkers, and the addition of task-specific functional groups including amines for CO 2 capture. As a canopy of polymeric chains was grafted onto the nanoparticle cores, the thermal stability of the resulting NOHMs was improved. In order to isolate the entropy effect during CO 2 capture, NOHMs were first prepared using polymers that do not contain functional groups with strong chemical affinity toward CO 2. However, it was found that even ether groups on the polymeric canopy contributed to CO 2 capture in NOHMs via Lewis acid-base interactions, although this effect was insignificant compared to the effect of task-specific functional groups such as amine. In all cases, a higher partial pressure of CO 2 was more favorable for CO 2 capture, while a higher temperature caused an adverse effect. Multicyclic CO 2 capture tests confirmed superior recyclability of NOHMs and NOHMs also showed a higher selectivity toward CO 2 over N 2O, O 2 and N 2. © 2011 American Chemical Society.

  15. Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

    Energy Technology Data Exchange (ETDEWEB)

    Colby, Denise; Bergman, Robert; Ellman, Jonathan

    2010-05-13

    Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

  16. A Transtextual Approach to Lexicographic Functions | Gouws | Lexikos

    African Journals Online (AJOL)

    The development of theoretical lexicography clearly indicates a movement towards a more general recognition of the role of lexicographic functions. A consistent application of lexico-graphic functions has a major influence on the contents of dictionary articles but also on the data distribution and even the typological ...

  17. Measurement of dynamic efficiency: a directional distance function parametric approach

    NARCIS (Netherlands)

    Serra, T.; Oude Lansink, A.G.J.M.; Stefanou, S.E.

    2011-01-01

    This research proposes a parametric estimation of the structural dynamic efficiency measures proposed by Silva and Oude Lansink (2009). Overall, technical and allocative efficiency measurements are derived based on a directional distance function and the duality between this function and the optimal

  18. Persuading by addressing: a functional approach to speech-act ...

    African Journals Online (AJOL)

    The phatic function, which, according to Jakobson (1960), provides the appropriate channel for communication, is of particular importance in this respect. If the channel does not work properly, the persuasive function will never fulfil its aim. In the following paper, a small corpus of English, Spanish and German advertising ...

  19. The Motivational Function of Private Speech: An Experimental Approach.

    Science.gov (United States)

    de Dios, M. J.; Montero, I.

    Recently, some works have been published exploring the role of private speech as a tool for motivation, reaching beyond the classical research on its regulatory function for cognitive processes such as attention or executive function. In fact, the authors' own previous research has shown that a moderate account of spontaneous private speech of…

  20. COSMETICS AS THEMATIC TO APPROACH ORGANIC FUNCTIONS IN CHEMISTRY TEACHING

    OpenAIRE

    FREITAS, Tasielle Lima; DA COSTA, Maria Aparecida; FREITAS, Fabricia Carla Ribeiro Mendes; OLIVEIRA, Tatiana de Fátima; MORAES, Lilian Marciolina; FIELD’S, Karla Amâncio Pinto; REZENDE, Gláucia Aparecida Andrade; SANTOS, Renato Gomes

    2016-01-01

    The science teaching has become more complex each passing day regarding its approach in an attempt to promote a more effective content learning, what requires from the teachers reflection concerning their education teaching, aiming at the use of different teaching strategies, such as the approach of chemistry contents through their relation to a social context in which they are inserted, as the use of cosmetics. This paper reports on a pedagogical intervention project in the subject of Sup...

  1. Advances in the indirect, descriptive, and experimental approaches to the functional analysis of problem behavior.

    Science.gov (United States)

    Wightman, Jade; Julio, Flávia; Virués-Ortega, Javier

    2014-05-01

    Experimental functional analysis is an assessment methodology to identify the environmental factors that maintain problem behavior in individuals with developmental disabilities and in other populations. Functional analysis provides the basis for the development of reinforcement-based approaches to treatment. This article reviews the procedures, validity, and clinical implementation of the methodological variations of functional analysis and function-based interventions. We present six variations of functional analysis methodology in addition to the typical functional analysis: brief functional analysis, single-function tests, latency-based functional analysis, functional analysis of precursors, and trial-based functional analysis. We also present the three general categories of function-based interventions: extinction, antecedent manipulation, and differential reinforcement. Functional analysis methodology is a valid and efficient approach to the assessment of problem behavior and the selection of treatment strategies.

  2. Nature and strength of bonding in a crystal of semiconducting nanotubes: van der Waals density functional calculations and analytical results

    DEFF Research Database (Denmark)

    Kleis, Jesper; Schröder, Elsebeth; Hyldgaard, Per

    2008-01-01

    for the nanotube-crystal binding energy can be approximated by a sum of nanotube-pair interactions when these are calculated in vdW-DR This observation suggests a framework for an efficient implementation of quantum-physical modeling of the carbon nanotube bundling in more general nanotube bundles, including...... nanotube yarn and rope structures.......The dispersive interaction between nanotubes is investigated through ab initio theory calculations and in an analytical approximation. A van der Waals density functional (vdW-DF) [M. Dion et al., Phys. Rev. Lett. 92, 246401 (2004)] is used to determine and compare the binding of a pair of nanotubes...

  3. A genetic approach to understanding asthma and lung function development

    DEFF Research Database (Denmark)

    Kreiner-Møller, Eskil

    2014-01-01

    Asthma is a common heritable disease of the airways with recurrent episodes of symptoms and reversible airflow obstruction that has increased dramatically in prevalence. The disease is highly heterogeneous with varying age at onset and clinical presentation and most likely represents several...... their effect. In paper I, we investigated the known effect of adult lung function loci on the development of lung function and bronchial responsiveness in children from birth until 7 years of age in the COPSAC2000 birth cohort of 411 children. We measured lung function and bronchial responsiveness at one month...... of age using the raised volume rapid thoracoabdominal compression technique in sedated neonates and repeated the measurements at age 7 utilizing traditional spirometry assessments. Lung function genetic variants identified in adults were not associated with neonatal lung function or bronchial...

  4. SOCIAL BONDING: REGULATION BY NEUROPEPTIDES

    Directory of Open Access Journals (Sweden)

    Claudia eLieberwirth

    2014-06-01

    Full Text Available Affiliative social relationships (e.g., among spouses, family members, and friends play an essential role in human society. These relationships affect psychological, physiological, and behavioral functions. As positive and enduring bonds are critical for the overall well-being of humans, it is not surprising that considerable effort has been made to study the neurobiological mechanisms that underlie social bonding behaviors. The present review details the involvement of the nonapeptides, oxytocin (OT and arginine vasopressin (AVP, in the regulation of social bonding in mammals including humans. In particular, we will discuss the role of OT and AVP in the formation of social bonds between partners of a mating pair as well as between parents and their offspring. Furthermore, the role of OT and AVP in the formation of interpersonal bonding involving trust is also discussed.

  5. Reduction of unsaturated compounds under interstellar conditions: chemoselective reduction of C≡C and C=C bonds over C=O functional group

    Science.gov (United States)

    Jonusas, Mindaugas; Guillemin, Jean-Claude; Krim, Lahouari

    2017-07-01

    The knowledge of the H-addition reactions on unsaturated organic molecules bearing a triple or a double carbon-carbon bond such as propargyl or allyl alcohols and a CO functional group such as propynal, propenal or propanal may play an important role in the understanding of the chemical complexity of the interstellar medium. Why different aldehydes like methanal, ethanal, propynal and propanal are present in dense molecular clouds while the only alcohol detected in those cold regions is methanol? In addition, ethanol has only been detected in hot molecular cores. Are those saturated and unsaturated aldehyde and alcohol species chemically linked in molecular clouds through solid phase H-addition surface reactions or are they formed through different chemical routes? To answer such questions, we have investigated a hydrogenation study of saturated and unsaturated aldehydes and alcohols at 10 K. We prove through this experimental study that while pure unsaturated alcohol ices bombarded by H atoms lead to the formation of the corresponding fully or partially saturated alcohols, surface H-addition reactions on unsaturated aldehyde ices exclusively lead to the formation of fully saturated aldehyde. Such results show that in addition to a chemoselective reduction of C≡C and C=C bonds over the C=O group, there is no link between aldehydes and their corresponding alcohols in reactions involving H atoms in dense molecular clouds. Consequently, this could be one of the reasons why some aldehydes such as propanal are abundant in dense molecular clouds in contrast to the non-detection of alcohol species larger than methanol.

  6. Hexacoordinate bonding and aromaticity in silicon phthalocyanine.

    Science.gov (United States)

    Yang, Yang

    2010-12-23

    Si-E bondings in hexacoordinate silicon phthalocyanine were analyzed using bond order (BO), energy partition, atoms in molecules (AIM), electron localization function (ELF), and localized orbital locator (LOL). Bond models were proposed to explain differences between hexacoordinate and tetracoordinate Si-E bondings. Aromaticity of silicon phthalocyanine was investigated using nucleus-independent chemical shift (NICS), harmonic oscillator model of aromaticity (HOMA), conceptual density functional theory (DFT), ring critical point (RCP) descriptors, and delocalization index (DI). Structure, energy, bonding, and aromaticity of tetracoordinate silicon phthalocyanine were studied and compared with hexacoordinate one.

  7. A3-Coupling catalyzed by robust Au nanoparticles covalently bonded to HS-functionalized cellulose nanocrystalline films

    Directory of Open Access Journals (Sweden)

    Jian-Lin Huang

    2013-07-01

    Full Text Available We decorated HS-functionalized cellulose nanocrystallite (CNC films with monodisperse Au nanoparticles (AuNPs to form a novel nanocomposite catalyst AuNPs@HS-CNC. The uniform, fine AuNPs were made by the reduction of HAuCl4 solution with thiol (HS- group-functionalized CNC films. The AuNPs@HS-CNC nanocomposites were examined by X-ray photoelectron spectroscopy (XPS, TEM, ATR-IR and solid-state NMR. Characterizations suggested that the size of the AuNPs was about 2–3 nm and they were evenly distributed onto the surface of CNC films. Furthermore, the unique nanocomposite Au@HS-CNC catalyst displayed high catalytic efficiency in promoting three-component coupling of an aldehyde, an alkyne, and an amine (A3-coupling either in water or without solvent. Most importantly, the catalyst could be used repetitively more than 11 times without significant deactivation. Our strategy also promotes the use of naturally renewable cellulose to prepare reusable nanocomposite catalysts for organic synthesis.

  8. Enhancement of biodiversity in energy farming: towards a functional approach

    International Nuclear Information System (INIS)

    Londo, M.; Dekker, J.

    1997-01-01

    When biomass is a substantial sustainable energy source, and special energy crops are grown on a large scale, land use and the environment of agriculture will be affected. Of these effects, biodiversity deserves special attention. The enhancement of biodiversity in energy farming via standard setting is the overall purpose of this project. In this study, the potential functionality of biodiversity in energy farming is proposed as a way of operationalising the rather abstract and broad concept of biodiversity. Functions of biodiversity are reviewed, and examples of functions are worked out, based on the current literature of nature in energy farming systems. (author)

  9. The chemisorptive bond basic concepts

    CERN Document Server

    Clark, Alfred

    1974-01-01

    The Chemisorptive Bond: Basic Concepts describes the basic concepts of the chemisorptive bond on solid surfaces from the simple analogies with ordinary chemical bonds to the quantum-mechanical approaches.This book is composed of 10 chapters and begins with discussions of simple formulas for correlating measurable quantities in chemisorptions and catalysis. The succeeding chapters deal with theories based on quantum-mechanical principles that describe the mutual interactions of atoms of the solid and foreign atoms on the surface. The remaining chapters consider the possible arrangements

  10. The basis function approach for modeling autocorrelation in ecological data.

    Science.gov (United States)

    Hefley, Trevor J; Broms, Kristin M; Brost, Brian M; Buderman, Frances E; Kay, Shannon L; Scharf, Henry R; Tipton, John R; Williams, Perry J; Hooten, Mevin B

    2017-03-01

    Analyzing ecological data often requires modeling the autocorrelation created by spatial and temporal processes. Many seemingly disparate statistical methods used to account for autocorrelation can be expressed as regression models that include basis functions. Basis functions also enable ecologists to modify a wide range of existing ecological models in order to account for autocorrelation, which can improve inference and predictive accuracy. Furthermore, understanding the properties of basis functions is essential for evaluating the fit of spatial or time-series models, detecting a hidden form of collinearity, and analyzing large data sets. We present important concepts and properties related to basis functions and illustrate several tools and techniques ecologists can use when modeling autocorrelation in ecological data. © 2016 by the Ecological Society of America.

  11. Chemical Pressure Maps of Molecules and Materials: Merging the Visual and Physical in Bonding Analysis.

    Science.gov (United States)

    Osman, Hussien H; Salvadó, Miguel A; Pertierra, Pilar; Engelkemier, Joshua; Fredrickson, Daniel C; Recio, J Manuel

    2018-01-09

    The characterization of bonding interactions in molecules and materials is one of the major applications of quantum mechanical calculations. Numerous schemes have been devised to identify and visualize chemical bonds, including the electron localization function, quantum theory of atoms in molecules, and natural bond orbital analysis, whereas the energetics of bond formation are generally analyzed in qualitative terms through various forms of energy partitioning schemes. In this Article, we illustrate how the chemical pressure (CP) approach recently developed for analyzing atomic size effects in solid state compounds provides a basis for merging these two approaches, in which bonds are revealed through the forces of attraction and repulsion acting between the atoms. Using a series of model systems that include simple molecules (H 2 , CO 2 , and S 8 ), extended structures (graphene and diamond), and systems exhibiting intermolecular interactions (ice and graphite), as well as simple representatives of metallic and ionic bonding (Na and NaH, respectively), we show how CP maps can differentiate a range of bonding phenomena. The approach also allows for the partitioning of the potential and kinetic contributions to the interatomic interactions, yielding schemes that capture the physical model for the chemical bond offered by Ruedenberg and co-workers.

  12. Vibrational spectra, molecular structure, natural bond orbital, first order hyperpolarizability, thermodynamic analysis and normal coordinate analysis of Salicylaldehyde p-methylphenylthiosemicarbazone by density functional method

    Science.gov (United States)

    Porchelvi, E. Elamurugu; Muthu, S.

    2015-01-01

    The thiosemicarbazone compound, Salicylaldehyde p-methylphenylthiosemicarbazone (abbreviated as SMPTSC) was synthesized and characterized by FTIR, FT-Raman and UV. Density functional (DFT) calculations have been carried out for the title compound by performing DFT level of theory using B3LYP/6-31++G(d,p) basis set. The molecular geometry and vibrational frequencies were calculated and compared with the experimental data. The detailed interpretation of the vibrational spectra has been carried out with aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology. The electronic dipole moment (μD) and the first hyperpolarizability (βtot) values of the investigated molecule were computed using density functional theory (DFT/B3LYP) with 6-311++G(d,p) basis set. The stability and charge delocalization of the molecule was studied by natural bond orbital (NBO) analysis. Thearomaticities of the phenyl rings were studied using the standard harmonic oscillator model of aromaticity (HOMA) index. Mulliken population analysis on atomic charges is also calculated. The molecule orbital contributions are studied by density of energy states (DOSs).

  13. Unified many-body approach to van der Waals interactions based on semi-local polarizability functional

    Science.gov (United States)

    Hermann, Jan; Scheffler, Matthias; Tkatchenko, Alexandre

    Electromagnetic coupling of charge fluctuations leads to van der Waals (vdW) attraction in systems ranging from metal nanoparticles to dielectric materials. In this regard, broadly applicable and accurate description of vdW interactions in complex materials is an elusive and unsolved puzzle. Many promising approaches model various subsets of this general problem, but are limited in scope by the underlying parametrization (atomic models), in accuracy due to missing many-body interactions (nonlocal density functionals), or in efficiency by working with virtual orbital space (e.g., random-phase approximation). Here, we present a unifying method that combines key elements from different theories and accurately describes vdW interactions in covalent, ionic, and metallic systems. In particular, we employ a semi-local polarizability functional of the electron density and its gradient to parametrize material response and its coupling within the many-body dispersion framework, and demonstrate the generality of the method on binding in molecular dimers and crystals, carbon-based nanomaterials, oxides, and salts, as well as on adsorption of molecules on metal surfaces. Our approach allows consistent modelling of a wide spectrum of materials as well as hybrid materials with mixed bond types.

  14. Efficient wave-function matching approach for quantum transport calculations

    DEFF Research Database (Denmark)

    Sørensen, Hans Henrik Brandenborg; Hansen, Per Christian; Petersen, Dan Erik

    2009-01-01

    . This approach makes it feasible to apply iterative techniques to efficiently determine the few required bulk modes, which allows for a significant reduction of the computational expense of the WFM method. We illustrate the efficiency of the method on a carbon nanotube field-effect-transistor device displaying...... band-to-band tunneling and modeled within the semiempirical extended Hückel theory framework....

  15. Approaches to organizing public relations functions in healthcare.

    Science.gov (United States)

    Guy, Bonnie; Williams, David R; Aldridge, Alicia; Roggenkamp, Susan D

    2007-01-01

    This article provides health care audiences with a framework for understanding different perspectives of the role and functions of public relations in healthcare organizations and the resultant alternatives for organizing and enacting public relations functions. Using an example of a current issue receiving much attention in US healthcare (improving rates of organ donation), the article provides examples of how these different perspectives influence public relations goals and objectives, definitions of 'public', activities undertaken, who undertakes them and where they fit into the organizational hierarchy.

  16. Mayer Transfer Operator Approach to Selberg Zeta Function

    DEFF Research Database (Denmark)

    Momeni, Arash; Venkov, Alexei

    These notes are based on three lectures given by the second author at Copenhagen University (October 2009) and at Aarhus University, Denmark (December 2009). We mostly present here a survey of results of Dieter Mayer on relations between Selberg and Smale-Ruelle dynamical zeta functions. In a spe......These notes are based on three lectures given by the second author at Copenhagen University (October 2009) and at Aarhus University, Denmark (December 2009). We mostly present here a survey of results of Dieter Mayer on relations between Selberg and Smale-Ruelle dynamical zeta functions...

  17. Lee-Wick indefinite metric quantization: A functional integral approach

    International Nuclear Information System (INIS)

    Boulware, D.G.; Gross, D.J.

    1984-01-01

    In an attempt to study the stability of the Lee-Wick indefinite metric theory, the functional integral for indefinite metric quantum field theories is derived. Theories with an indefinite classical energy may be quantized with either a normal metric and an indefinite energy in Minkowski space or an indefinite metric and a positive energy in euclidean space. However, the functional integral in the latter formulation does not incorporate the Lee-Wick prescription for assuring the unitarity of the positive energy positive metric sector of the theory, hence the stability of the theory cannot be studied non-perturbatively. (orig.)

  18. Synergetic approach of norm and pathology of living system functioning

    International Nuclear Information System (INIS)

    Asqarov, B.; Oksengendler, B.L.; Turaeva, N.N.; Karimov, Z.; Rafikova, Z.B.

    2011-01-01

    Basing on fundamental idea of dynamical chaos and strict periodicity in living systems the new peculiarities in brain and heart functioning have been reveled. It has been shown that the development of pathological states of brain and heart activities occurs by means of both increase and decrease of chaos components in brain activity and heart rhythm. It has been defined the 'health range' for brain and heart functioning in norm, and the method of recovery of the health range is proposed from the electrocardiograms and electroencephalograms data (authors).

  19. Understanding Bonds - Denmark

    DEFF Research Database (Denmark)

    Rimmer, Nina Røhr

    2016-01-01

    a specified rate of interest during the life of the bond and to repay the face value of the bond (the principal) when it “matures,” or comes due. Among the types of bonds you can choose from are: Government securities, municipal bonds, corporate bonds, mortgage and asset-backed securities, federal agency...

  20. Teaching Mathematical Functions Using Geometric Functions Approach and Its Effect on Ninth Grade Students' Motivation

    Science.gov (United States)

    Akçakin, Veysel

    2018-01-01

    The purpose of this study is to investigate the effects of using geometric functions approach on 9th grade students' motivation levels toward mathematics in functions unit. Participants of this study were 87 students who were ongoing in the first year of high school in Turkey. In this research, pretest and posttest control group quasiexperimental…

  1. General atomistic approach for modeling metal-semiconductor interfaces using density functional theory and nonequilibrium Green's function

    DEFF Research Database (Denmark)

    Stradi, Daniele; Martinez, Umberto; Blom, Anders

    2016-01-01

    an atomistic approach based on density functional theory and nonequilibrium Green's function, which includes all the relevant ingredients required to model realistic metal-semiconductor interfaces and allows for a direct comparison between theory and experiments via I-Vbias curve simulations. We apply...

  2. Newer Approaches to Identify Potential Untoward Effects in Functional Foods.

    Science.gov (United States)

    Marone, Palma Ann; Birkenbach, Victoria L; Hayes, A Wallace

    2016-01-01

    Globalization has greatly accelerated the numbers and variety of food and beverage products available worldwide. The exchange among greater numbers of countries, manufacturers, and products in the United States and worldwide has necessitated enhanced quality measures for nutritional products for larger populations increasingly reliant on functionality. These functional foods, those that provide benefit beyond basic nutrition, are increasingly being used for their potential to alleviate food insufficiency while enhancing quality and longevity of life. In the United States alone, a steady import increase of greater than 15% per year or 24 million shipments, over 70% products of which are food related, is regulated under the Food and Drug Administration (FDA). This unparalleled growth has resulted in the need for faster, cheaper, and better safety and efficacy screening methods in the form of harmonized guidelines and recommendations for product standardization. In an effort to meet this need, the in vitro toxicology testing market has similarly grown with an anticipatory 15% increase between 2010 and 2015 of US$1.3 to US$2.7 billion. Although traditionally occupying a small fraction of the market behind pharmaceuticals and cosmetic/household products, the scope of functional food testing, including additives/supplements, ingredients, residues, contact/processing, and contaminants, is potentially expansive. Similarly, as functional food testing has progressed, so has the need to identify potential adverse factors that threaten the safety and quality of these products. © The Author(s) 2015.

  3. A Bioinformatic Approach to Inter Functional Interactions within Protein Sequences

    Science.gov (United States)

    2009-02-23

    cell division genes in Eubacteria, and ribosomal genes in Eubacteria and Eukaryotic organelles. Genetica 2000, 108(1):1-7. 9. Altschul SF, Gish W...functional domains of serpin proteins. Molecular Biology and Evolution, 2005. 22: 1627-1634. 3. Codoner, F.M. & M.A. Fares, Why should we care about

  4. The electron-propagator approach to conceptual density-functional ...

    Indian Academy of Sciences (India)

    Unknown

    (4), the external potential is fixed by identity of the molecular system and is thus treated as a parameter and not a variable. Equation (4) is an exact expres- sion for the ...... the virtual spin-orbitals, and {χp} is a set of ortho- normal basis functions. The expression for the third- order correction is more complicated. Because the.

  5. Filling the gap between sequence and function: a bioinformatics approach

    NARCIS (Netherlands)

    Bargsten, J.W.

    2014-01-01

    The research presented in this thesis focuses on deriving function from sequence information, with the emphasis on plant sequence data. Unravelling the impact of genomic elements, in most cases genes, on the phenotype of an organism is a major challenge in biological research and modern plant

  6. The electron-propagator approach to conceptual density-functional ...

    Indian Academy of Sciences (India)

    Unknown

    Abstract. Both electron propagator theory and density-functional theory provide conceptually useful information about chemical reactivity and, most especially, charge transfer. This paper elucidates the qualitative and quantitative links between the two theories, with emphasis on how the reactivity indica- tors of conceptual ...

  7. A Derivational Approach to the Operational Semantics of Functional Languages

    DEFF Research Database (Denmark)

    Biernacka, Malgorzata

    We study the connections between different forms of operational semantics for functional programming languages and we present systematic methods of interderiving reduction semantics, abstract machines and higher-order evaluators. We first consider two methods based on program transformations: a s...

  8. The electron-propagator approach to conceptual density-functional ...

    Indian Academy of Sciences (India)

    Both electron propagator theory and density-functional theory provide conceptually useful information about chemical reactivity and, most especially, charge transfer. This paper elucidates thequalitative and quantitative links between the two theories, with emphasis on how the reactivity indicators of conceptual ...

  9. Filling the gap between sequence and function: a bioinformatics approach

    NARCIS (Netherlands)

    Bargsten, J.W.

    2014-01-01

    The research presented in this thesis focuses on deriving function from sequence information, with the emphasis on plant sequence data. Unravelling the impact of genomic elements, in most cases genes, on the phenotype of an organism is a major challenge in biological research and modern plant

  10. Functional Problems of the Visually Impaired: A Research Approach.

    Science.gov (United States)

    Bikson, Thomas H.; Bikson, Tora K.

    Capabilities and limitations of 251 severely visually impaired persons (senior high school age or older) were assessed on a range of visual environmental adaptation problems to learn how they are organized and influenced. Factor analyses indicated that problems can be grouped on the basis of eight functional domains, among which an independent…

  11. Functional brain laterality in adulthood ADHD : A dimensional approach

    NARCIS (Netherlands)

    Mohamed, Saleh

    2017-01-01

    The present thesis aimed to address functional brain laterality and symptoms of Attention-Deficit/Hyperactivity Disorder (ADHD) in adults, from a dimensional perspective. The dimensional perspective assumes that ADHD symptoms are normally distributed in general population and those scoring at the

  12. Approaching TERRA Firma: Genomic Functions of Telomeric Noncoding RNA.

    Science.gov (United States)

    Roake, Caitlin M; Artandi, Steven E

    2017-06-29

    Functions of the telomeric repeat-containing RNA (TERRA), the long noncoding RNA (lncRNA) transcribed from telomeres, have eluded researchers. In this issue of Cell, Graf el al. and Chu et al. uncover new regulatory roles for TERRA at the telomere and at distant genomic sites. Copyright © 2017 Elsevier Inc. All rights reserved.

  13. A crystal chemistry approach for high-power ytterbium doped solid-state lasers: diffusion-bonded crystals and new crystalline hosts

    International Nuclear Information System (INIS)

    Gaume, R.

    2002-11-01

    This work deals with ytterbium based crystals for high-power laser applications. In particular, we focus our interest in reducing crystal heating and its consequences during laser operation following two different ways. First, we review the specific properties of ytterbium doped solid-state lasers in order to define a figure-of-merit which gives the evaluation of laser performances, thermo-mechanical and thermo-optical properties. Bearing in mind this analysis, we propose a set of theoretical tools, based on the crystallographic structure of the crystal and its chemical composition, to predict thermo-mechanical and optical potentials. This approach, used for the seek of new Yb 3+ -doped materials for high-power laser applications, shows that simple oxides containing rare-earths are favorable. Therefore, the spectroscopic properties of six new materials Yb 3+ :GdVO 4 , Yb 3+ :GdAlO 3 , Yb 3+ :Gd 2 O 3 , Yb 3+ :Sc 2 SiO 5 , Yb 3+ :CaSc 2 O 4 and Yb 3+ :SrSc 2 O 4 are described. The second aspect developed in this work deals with thermal properties enhancement of already well characterized laser materials. Two different ways are explored: a) elaboration by diffusion bonding of end-caps lasers with undoped crystals (composite crystals). Thus, different composites were obtained and a fairly lowering of thermal lensing effect was observed during laser operation. b) strengthening of crystalline structures by ionic substitution of one of its constituents. We demonstrate how crystal growth ability can be improved by a cationic substitution in the case of Yb 3+ :BOYS, a largely-tunable laser material which is of great interest for femtosecond pulses generation. (author)

  14. A Functional Approach to Hyperspectral Image Analysis in the Cloud

    Science.gov (United States)

    Wilson, A.; Lindholm, D. M.; Coddington, O.; Pilewskie, P.

    2017-12-01

    Hyperspectral image volumes are very large. A hyperspectral image analysis (HIA) may use 100TB of data, a huge barrier to their use. Hylatis is a new NASA project to create a toolset for HIA. Through web notebook and cloud technology, Hylatis will provide a more interactive experience for HIA by defining and implementing concepts and operations for HIA, identified and vetted by subject matter experts, and callable within a general purpose language, particularly Python. Hylatis leverages LaTiS, a data access framework developed at LASP. With an OPeNDAP compliant interface plus additional server side capabilities, the LaTiS API provides a uniform interface to virtually any data source, and has been applied to various storage systems, including: file systems, databases, remote servers, and in various domains including: space science, systems administration and stock quotes. In the LaTiS architecture, data `adapters' read data into a data model, where server-side computations occur. Data `writers' write data from the data model into the desired format. The Hylatis difference is the data model. In LaTiS, data are represented as mathematical functions of independent and dependent variables. Domain semantics are not present at this level, but are instead present in higher software layers. The benefit of a domain agnostic, mathematical representation is having the power of math, particularly functional algebra, unconstrained by domain semantics. This agnosticism supports reusable server side functionality applicable in any domain, such as statistical, filtering, or projection operations. Algorithms to aggregate or fuse data can be simpler because domain semantics are separated from the math. Hylatis will map the functional model onto the Spark relational interface, thereby adding a functional interface to that big data engine.This presentation will discuss Hylatis goals, strategies, and current state.

  15. Urea functionalized surface-bonded sol-gel coating for on-line hyphenation of capillary microextraction with high-performance liquid chromatography.

    Science.gov (United States)

    Jillani, Shehzada Muhammad Sajid; Alhooshani, Khalid

    2018-03-30

    Sol-gel urea functionalized-[bis(hydroxyethyl)amine] terminated polydimethylsiloxane coating was developed for capillary microextraction-high performance liquid chromatographic analysis from aqueous samples. A fused silica capillary is coated from the inside with surface bonded coating material and is created through in-situ sol-gel reaction. The urea-functionalized coating was immobilized to the inner surface of the capillary by the condensation reaction of silanol groups of capillary and sol-solution. The characterization of the coating material was successfully done by using X-ray photoelectron spectroscopy, thermogravimetric analysis, field emission scanning electron microscope, and energy dispersive X-ray spectrometer. To make a setup of online capillary microextraction-high performance liquid chromatography, the urea functionalized capillary was installed in the HPLC manual injection port. The analytes of interest were pre-concentrated in the coated sampling loop, desorbed by the mobile phase, chromatographically separated on C-18 column, and analyzed by UV detector. Sol-gel coated capillaries were used for online extraction and high-performance liquid chromatographic analysis of phenols, ketones, aldehydes, and polyaromatic hydrocarbons. This newly developed coating showed excellent extraction for a variety of analytes ranging from highly polar to non-polar in nature. The analysis using sol-gel coating showed excellent overall sensitivity in terms of lower detection limits (S/N = 3) for the analytes (0.10 ng mL -1 -14.29 ng mL -1 ) with acceptable reproducibility that is less than 12.0%RSD (n = 3). Moreover, the capillary to capillary reproducibility of the analysis was also tested by changing the capillary of the same size. This provided excellent%RSD of less than 10.0% (n = 3). Copyright © 2018 Elsevier B.V. All rights reserved.

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

    Science.gov (United States)

    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.

  17. A hybrid fuzzy MCDM approach to maintenance Quality Function Deployment

    Directory of Open Access Journals (Sweden)

    Davy George Valavi

    2015-01-01

    Full Text Available Maintenance Quality Function Deployment (MQFD is a model, which enhances the synergic power of Quality Function Deployment (QFD and Total Productive Maintenance (TPM. One of the crucial and important steps during the implementation of MQFD is the determination of the importance or weightages of the critical factors (CF and sub factors (SF. The CFs and SFs have to be compared precisely for the successful implementation of MQFD. The crisp pair-wise comparison in the conventional Analytical Hierarchy Process (AHP may be insufficient to determine the degree of weightage of CFs and SFs where vagueness and uncetainties are associated. In this paper, a modification of AHP based MQFD by incorporating fuzzy operations is proposed, which can improve the accuracy of determination of the weightages. A case study showing the applicability of this method is illustrated in this paper.

  18. Alternative approach for establishing the Nacelle Transfer Function

    DEFF Research Database (Denmark)

    Krishna, Vinay B.; Ormel, Frank; Hansen, Kurt Schaldemose

    2016-01-01

    -consistency checks have failed to meet the criteria listed in the standard. The root cause analysis against such failure showed that the methodology followed by the standard is less accurate in estimating the free stream wind speed. Suitable changes were made in the process of establishing the nacelle transfer...... will be strongly affected by the wind turbine’s rotor and the nacelle. Suitable correction against such flow distortion is applied through a nacelle transfer function (NTF). The -12-2standard requires a self-consistency check performed on such established NTF using the nacelle power curve. Most of these self...... function and the subsequent self-consistency checks were found to be clearing the criteria set by the standard....

  19. Configuration interaction wave functions: A seniority number approach

    Energy Technology Data Exchange (ETDEWEB)

    Alcoba, Diego R. [Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires and Instituto de Física de Buenos Aires, Consejo Nacional de Investigaciones Científicas y Técnicas, Ciudad Universitaria, 1428 Buenos Aires (Argentina); Torre, Alicia; Lain, Luis, E-mail: qfplapel@lg.ehu.es [Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco, Apdo. 644, E-48080 Bilbao (Spain); Massaccesi, Gustavo E. [Departamento de Ciencias Exactas, Ciclo Básico Común, Universidad de Buenos Aires, Ciudad Universitaria, 1428 Buenos Aires (Argentina); Oña, Ofelia B. [Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas, Universidad Nacional de La Plata, CCT La Plata, Consejo Nacional de Investigaciones Científicas y Técnicas, Diag. 113 y 64 (S/N), Sucursal 4, CC 16, 1900 La Plata (Argentina)

    2014-06-21

    This work deals with the configuration interaction method when an N-electron Hamiltonian is projected on Slater determinants which are classified according to their seniority number values. We study the spin features of the wave functions and the size of the matrices required to formulate states of any spin symmetry within this treatment. Correlation energies associated with the wave functions arising from the seniority-based configuration interaction procedure are determined for three types of molecular orbital basis: canonical molecular orbitals, natural orbitals, and the orbitals resulting from minimizing the expectation value of the N-electron seniority number operator. The performance of these bases is analyzed by means of numerical results obtained from selected N-electron systems of several spin symmetries. The comparison of the results highlights the efficiency of the molecular orbital basis which minimizes the mean value of the seniority number for a state, yielding energy values closer to those provided by the full configuration interaction procedure.

  20. Configuration interaction wave functions: A seniority number approach

    International Nuclear Information System (INIS)

    Alcoba, Diego R.; Torre, Alicia; Lain, Luis; Massaccesi, Gustavo E.; Oña, Ofelia B.

    2014-01-01

    This work deals with the configuration interaction method when an N-electron Hamiltonian is projected on Slater determinants which are classified according to their seniority number values. We study the spin features of the wave functions and the size of the matrices required to formulate states of any spin symmetry within this treatment. Correlation energies associated with the wave functions arising from the seniority-based configuration interaction procedure are determined for three types of molecular orbital basis: canonical molecular orbitals, natural orbitals, and the orbitals resulting from minimizing the expectation value of the N-electron seniority number operator. The performance of these bases is analyzed by means of numerical results obtained from selected N-electron systems of several spin symmetries. The comparison of the results highlights the efficiency of the molecular orbital basis which minimizes the mean value of the seniority number for a state, yielding energy values closer to those provided by the full configuration interaction procedure

  1. CONSTRUCTING AND DERIVING RECIPROCAL TRIGONOMETRIC RELATIONS: A FUNCTIONAL ANALYTIC APPROACH

    OpenAIRE

    Ninness, Chris; Dixon, Mark; Barnes-Holmes, Dermot; Rehfeldt, Ruth Anne; Rumph, Robin; McCuller, Glen; Holland, James; Smith, Ronald; Ninness, Sharon K; McGinty, Jennifer

    2009-01-01

    Participants were pretrained and tested on mutually entailed trigonometric relations and combinatorially entailed relations as they pertained to positive and negative forms of sine, cosine, secant, and cosecant. Experiment 1 focused on training and testing transformations of these mathematical functions in terms of amplitude and frequency followed by tests of novel relations. Experiment 2 addressed training in accordance with frames of coordination (same as) and frames of opposition (reciproc...

  2. Assessment of Thyroid Function: Towards an Integrated Laboratory - Clinical Approach

    OpenAIRE

    Stockigt, Jim

    2003-01-01

    Laboratory assessment of thyroid function is now often initiated with a low pre-test probability, by clinicians who may not have a detailed knowledge of current methodology or testing strategies. Skilled laboratory staff can significantly enhance the choice of appropriate tests and the accuracy of clinical response; such involvement requires both appropriate training and relevant information from the clinician. Measurement of the serum thyroid stimulating hormone (TSH) concentration with an a...

  3. Green-function approach to transport phenomena in quantum pumps

    Science.gov (United States)

    Arrachea, Liliana

    2005-09-01

    We present a general treatment based on nonequilibrium Green functions to study transport phenomena in systems described by tight-binding Hamiltonians coupled to reservoirs and with one or more time-periodic potentials. We apply this treatment to the study of transport phenomena in a double barrier structure with one and two ac potentials. Among other properties, we discuss the origin of the sign of the net current.

  4. Bonding in phase change materials: concepts and misconceptions.

    Science.gov (United States)

    Jones, R O

    2018-04-18

    Bonding concepts originating in chemistry are surveyed from a condensed matter perspective, beginning around 1850 with 'valence' and the word 'bond' itself. The analysis of chemical data in the 19th century resulted in astonishing progress in understanding the connectivity and stereochemistry of molecules, almost without input from physicists until the development of quantum mechanics in 1925 and afterwards. The valence bond method popularized by Pauling and the molecular orbital methods of Hund, Mulliken, Bloch, and Hückel play major roles in the subsequent development, as does the central part played by the kinetic energy in covalent bonding (Ruedenberg and others). 'Metallic' (free electron) and related approaches, including pseudopotential and density functional theories, have been remarkably successful in understanding structures and bonding in molecules and solids. We discuss these concepts in the context of phase change materials, which involve the rapid and reversible transition between amorphous and crystalline states, and note the confusion that some have caused, in particular 'resonance' and 'resonant bonding'.

  5. Preparation, Characterization and Mechanical Properties of Bio-Based Polyurethane Adhesives from Isocyanate-Functionalized Cellulose Acetate and Castor Oil for Bonding Wood

    Directory of Open Access Journals (Sweden)

    Adrián Tenorio-Alfonso

    2017-04-01

    Full Text Available Nowadays, different types of natural carbohydrates such as sugars, starch, cellulose and their derivatives are widely used as renewable raw materials. Vegetable oils are also considered as promising raw materials to be used in the synthesis of high quality products in different applications, including in the adhesive field. According to this, several bio-based formulations with adhesion properties were synthesized first by inducing the functionalization of cellulose acetate with 1,6-hexamethylene diisocyanate and then mixing the resulting biopolymer with a variable amount of castor oil, from 20% to 70% (wt. These bio-based adhesives were mechanically characterized by means of small-amplitude oscillatory torsion measurements, at different temperatures, and standardized tests to evaluate tension loading (ASTM-D906 and peel strength (ASTM-D903. In addition, thermal properties and stability of the synthesized bio-polyurethane formulations were also analyzed through differential scanning calorimetry and thermal gravimetric analysis. As a result, the performance of these bio-polyurethane products as wood adhesives were compared and analyzed. Bio-polyurethane formulations exhibited a simple thermo-rheological behavior below a critical temperature of around 80–100 °C depending on the castor oil/cellulose acetate weight ratio. Formulation with medium castor oil/biopolymer weight ratio (50:50 % wt showed the most suitable mechanical properties and adhesion performance for bonding wood.

  6. Change classification in SAR time series: a functional approach

    Science.gov (United States)

    Boldt, Markus; Thiele, Antje; Schulz, Karsten; Hinz, Stefan

    2017-10-01

    Change detection represents a broad field of research in SAR remote sensing, consisting of many different approaches. Besides the simple recognition of change areas, the analysis of type, category or class of the change areas is at least as important for creating a comprehensive result. Conventional strategies for change classification are based on supervised or unsupervised landuse / landcover classifications. The main drawback of such approaches is that the quality of the classification result directly depends on the selection of training and reference data. Additionally, supervised processing methods require an experienced operator who capably selects the training samples. This training step is not necessary when using unsupervised strategies, but nevertheless meaningful reference data must be available for identifying the resulting classes. Consequently, an experienced operator is indispensable. In this study, an innovative concept for the classification of changes in SAR time series data is proposed. Regarding the drawbacks of traditional strategies given above, it copes without using any training data. Moreover, the method can be applied by an operator, who does not have detailed knowledge about the available scenery yet. This knowledge is provided by the algorithm. The final step of the procedure, which main aspect is given by the iterative optimization of an initial class scheme with respect to the categorized change objects, is represented by the classification of these objects to the finally resulting classes. This assignment step is subject of this paper.

  7. Continuation of probability density functions using a generalized Lyapunov approach

    Energy Technology Data Exchange (ETDEWEB)

    Baars, S., E-mail: s.baars@rug.nl [Johann Bernoulli Institute for Mathematics and Computer Science, University of Groningen, P.O. Box 407, 9700 AK Groningen (Netherlands); Viebahn, J.P., E-mail: viebahn@cwi.nl [Centrum Wiskunde & Informatica (CWI), P.O. Box 94079, 1090 GB, Amsterdam (Netherlands); Mulder, T.E., E-mail: t.e.mulder@uu.nl [Institute for Marine and Atmospheric research Utrecht, Department of Physics and Astronomy, Utrecht University, Princetonplein 5, 3584 CC Utrecht (Netherlands); Kuehn, C., E-mail: ckuehn@ma.tum.de [Technical University of Munich, Faculty of Mathematics, Boltzmannstr. 3, 85748 Garching bei München (Germany); Wubs, F.W., E-mail: f.w.wubs@rug.nl [Johann Bernoulli Institute for Mathematics and Computer Science, University of Groningen, P.O. Box 407, 9700 AK Groningen (Netherlands); Dijkstra, H.A., E-mail: h.a.dijkstra@uu.nl [Institute for Marine and Atmospheric research Utrecht, Department of Physics and Astronomy, Utrecht University, Princetonplein 5, 3584 CC Utrecht (Netherlands); School of Chemical and Biomolecular Engineering, Cornell University, Ithaca, NY (United States)

    2017-05-01

    Techniques from numerical bifurcation theory are very useful to study transitions between steady fluid flow patterns and the instabilities involved. Here, we provide computational methodology to use parameter continuation in determining probability density functions of systems of stochastic partial differential equations near fixed points, under a small noise approximation. Key innovation is the efficient solution of a generalized Lyapunov equation using an iterative method involving low-rank approximations. We apply and illustrate the capabilities of the method using a problem in physical oceanography, i.e. the occurrence of multiple steady states of the Atlantic Ocean circulation.

  8. Approaching standard by designing a basic safety function

    OpenAIRE

    Baudoin , James; Bello , Jean-Paul

    2014-01-01

    This document is intended to guide designers to perform machinery control systems with only one or a few "basic safety functions such as emergency stop or movable guard.Among the available standards for machinery design, EN ISO 13849-1 is the one providing recommendations to design safety related parts of control systems (SRP/CS) implementing different types of energy such as electric, hydraulic or pneumatic.This document is based on the implementation of the simplified method of EN ISO 13849...

  9. Nuclear clustering in the energy density functional approach

    Energy Technology Data Exchange (ETDEWEB)

    Ebran, J.-P., E-mail: jean-paul.ebran@cea.fr [CEA,DAM,DIF, F-91297 Arpajon (France); Khan, E. [Institut de Physique Nucléaire, Université Paris-Sud CEA, IN2P3 CNRS, F-91406 Orsay Cedex (France); Nikšić, T.; Vretenar, D. [Physics Department, Faculty of Science, University of Zagreb, 10000 Zagreb (Croatia)

    2015-10-15

    Nuclear Energy Density Functionals (EDFs) are a microscopic tool of choice extensively used over the whole chart to successfully describe the properties of atomic nuclei ensuing from their quantum liquid nature. In the last decade, they also have proved their ability to deal with the cluster phenomenon, shedding a new light on its fundamental understanding by treating on an equal footing both quantum liquid and cluster aspects of nuclei. Such a unified microscopic description based on nucleonic degrees of freedom enables to tackle the question pertaining to the origin of the cluster phenomenon and emphasizes intrinsic mechanisms leading to the emergence of clusters in nuclei.

  10. Functional correlation approach to operational risk in banking organizations

    Science.gov (United States)

    Kühn, Reimer; Neu, Peter

    2003-05-01

    A Value-at-Risk-based model is proposed to compute the adequate equity capital necessary to cover potential losses due to operational risks, such as human and system process failures, in banking organizations. Exploring the analogy to a lattice gas model from physics, correlations between sequential failures are modeled by as functionally defined, heterogeneous couplings between mutually supportive processes. In contrast to traditional risk models for market and credit risk, where correlations are described as equal-time-correlations by a covariance matrix, the dynamics of the model shows collective phenomena such as bursts and avalanches of process failures.

  11. Reinforcing thermoplastics with hydrogen bonding bridged inorganics

    Energy Technology Data Exchange (ETDEWEB)

    Du Mingliang, E-mail: du@zstu.edu.c [Key Laboratory of Advanced Textile Materials and Manufacturing Technology, Ministry of Education, Zhejiang Sci-Tech University, Hangzhou 310018 (China); Guo Baochun, E-mail: psbcguo@scut.edu.c [Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou 510640 (China); Liu Mingxian; Cai Xiaojia; Jia Demin [Department of Polymer Materials and Engineering, South China University of Technology, Guangzhou 510640 (China)

    2010-01-15

    A new reinforcing strategy for thermoplastics via hydrogen bonding bridged inorganics in the matrix was proposed. The hydrogen bonds could be formed in thermoplastics matrices with the incorporation of a little organics containing hydrogen bonding functionalities. Isotactic polypropylene (PP), polyamide 6 (PA 6), and high density polyethylene (HDPE), together with specific inorganics and organics were utilized to verify the effectiveness of the strategy. The investigations suggest that the hydrogen bonding bridged inorganics led to substantially increased flexural properties. The results of attenuated total refraction Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectra (XPS) indicate the formation of hydrogen bonding among the inorganics and organics in the composites.

  12. Genomic and Functional Approaches to Understanding Cancer Aneuploidy.

    Science.gov (United States)

    Taylor, Alison M; Shih, Juliann; Ha, Gavin; Gao, Galen F; Zhang, Xiaoyang; Berger, Ashton C; Schumacher, Steven E; Wang, Chen; Hu, Hai; Liu, Jianfang; Lazar, Alexander J; Cherniack, Andrew D; Beroukhim, Rameen; Meyerson, Matthew

    2018-04-09

    Aneuploidy, whole chromosome or chromosome arm imbalance, is a near-universal characteristic of human cancers. In 10,522 cancer genomes from The Cancer Genome Atlas, aneuploidy was correlated with TP53 mutation, somatic mutation rate, and expression of proliferation genes. Aneuploidy was anti-correlated with expression of immune signaling genes, due to decreased leukocyte infiltrates in high-aneuploidy samples. Chromosome arm-level alterations show cancer-specific patterns, including loss of chromosome arm 3p in squamous cancers. We applied genome engineering to delete 3p in lung cells, causing decreased proliferation rescued in part by chromosome 3 duplication. This study defines genomic and phenotypic correlates of cancer aneuploidy and provides an experimental approach to study chromosome arm aneuploidy. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

  13. [System analytical approach of lung function and hemodynamics].

    Science.gov (United States)

    Naszlady, Attila; Kiss, Lajos

    2009-02-15

    The authors critically analyse the traditional views in physiology and complete them with new statements based on computer model simulations of lung function and of hemodynamics. Conclusions are derived for the clinical practice as follows: the four-dimensional function curves are similar in both systems; there is a "waterfall" zone in the pulmonary blood perfusion; the various time constants of pulmonary regions can modify the blood gas values; pulmonary capillary pressure is equal to pulmonary arterial diastole pressure; heart is not a pressure pump, but a flow source; ventricles are loaded by the input impedance of the arterial systems and not by the total vascular (ohmlike) resistance; optimum heart rate in rest depends on the length of the aorta; this law of heart rate, based on the principle of resonance is valid along the mammalian allometric line; tachycardia decreases the input impedance; using positive end expiratory pressure respirators the blood gas of pulmonary artery should be followed; coronary circulation should be assessed in beat per milliliter, the milliliter per minute may be false. These statements are compared to related references.

  14. [Sensory functions and Alzheimer's disease: a multi-disciplinary approach].

    Science.gov (United States)

    Kenigsberg, Paul-Ariel; Aquino, Jean-Pierre; Berard, Alain; Boucart, Muriel; Bouccara, Didier; Brand, Gérard; Charras, Kevin; Garcia-Larrea, Luis; Gzil, Fabrice; Krolak-Salmon, Pierre; Madjlessi, Arach; Malaquin-Pavan, Évelyne; Penicaud, Luc; Platel, Hervé; Pozzo, Thierry; Reintjens, Christophe; Salmon, Éric; Vergnon, Laurent; Robert, Philippe

    2015-09-01

    Relations between sensory functions and Alzheimer's disease are still under-explored. To understand them better, the Fondation Médéric Alzheimer has brought together a multi-disciplinary expert group. Aristote's five senses must be enhanced by today's knowledge of proprioception, motor cognition and pain perception. When cognition breaks down, the person with dementia perceives the world around her with her sensory experience, yet is unable to integrate all this information to understand the context. The treatment of multiple sensory inputs by the brain is closely linked to cognitive processes. Sensory deficits reduce considerably the autonomy of people with dementia in their daily life and their relations with others, increase their social isolation and the risk of accidents. Professionals involved with neurodegenerative diseases remain poorly aware of sensory deficits, which can bias the results of cognitive tests. However, there are simple tools to detect these deficits, notably for vision, hearing and balance disorders, which can be corrected. Many interventions for cognitive rehabilitation or quality of life improvement are based on sensory functions. The environment of people with dementia must be adapted to become understandable, comfortable, safe and eventually therapeutic.

  15. Polymer density functional approach to efficient evaluation of path integrals

    DEFF Research Database (Denmark)

    Brukhno, Andrey; Vorontsov-Velyaminov, Pavel N.; Bohr, Henrik

    2005-01-01

    A polymer density functional theory (P-DFT) has been extended to the case of quantum statistics within the framework of Feynman path integrals. We start with the exact P-DFT formalism for an ideal open chain and adapt its efficient numerical solution to the case of a ring. We show that, similarly......, the path integral problem can, in principle, be solved exactly by making use of the two-particle pair correlation function (2p-PCF) for the ends of an open polymer, half of the original. This way the exact data for one-dimensional quantum harmonic oscillator are reproduced in a wide range of temperatures....... The exact solution is not, though, reachable in three dimensions (3D) because of a vast amount of storage required for 2p-PCF. In order to treat closed paths in 3D, we introduce a so-called "open ring" approximation which proves to be rather accurate in the limit of long chains. We also employ a simple self...

  16. Density functional approach to the many-body problem : Key concepts and exact functionals

    NARCIS (Netherlands)

    van Leeuwen, Robert

    2003-01-01

    We give an overview of the fundamental concepts of density functional theory. We give a careful discussion of the several density functionals and their differentiability properties. We show that for nondegenerate ground states we can calculate the necessary functional derivatives by means of linear

  17. VISUALIZATION APPROACH TO STRUCTURE-FUNCTION RELATIONSHIP IN BIOLOGICAL MACROMOLECULES

    Directory of Open Access Journals (Sweden)

    M. Luetić

    2015-08-01

    Full Text Available Introduction: Most of recent research in the field of education strongly recommends the use of visualization in the daily teacher’s practice, especially when it comes to teaching science. Objectives: We investigated the impact of different kinds of visualization on student’s accomplishments, and the relationship between 2D and 3D visualization on the learning outcomes in biochemistry teaching, as well as gender-related differences in 2D vs 3D perception abilities. Materials and Methods: The research study was conducted on a sample of 149 senior secondary school students, devided into three groups: control group (usual teaching approach, and two experimental groups taught using different kinds of visualization: E1 (2D and 3D static visualization tools, and E2 (3D dynamic visualization tools, in addition. Discussion and results: We measured the students’ learning outcomes in biochemistry, as well as the level of satisfaction with different teaching methods. The data were interpreted by performing statistical measures and analyses. In order to validate our hypothesis, we used one-tail and two-tail ANOVA analyses (along with the t-test.Conclusions: There was no statistical significance regarding 2D vs 3D visualization tools in biochemistry teaching. Although there existed some gender-related differences in students’ achievements (in favor of females, it was not established that they were related to the type of visualization (2D or 3D tools applied. However students from the E2 group (additional computer animations were more interested and involved in this kind of teaching. Although the results do not show a statistical significance in favor of 3D visualization, we must conclude that in teaching biochemistry it is certainly a more efficient approach than traditional teacher-oriented lessons. By using this kind of visualization tools in everyday teaching practice, chemistry teachers are given the opportunity to enlighten students with somewhat

  18. Orbital localization criterion as a complementary tool in the bonding analysis by means of electron localization function: study of the Si(n)(BH)(5-n)(2-) (n = 0-5) clusters.

    Science.gov (United States)

    Oña, Ofelia B; Alcoba, Diego R; Torre, Alicia; Lain, Luis; Torres-Vega, Juan J; Tiznado, William

    2013-12-05

    A recently proposed molecular orbital localization procedure, based on the electron localization function (ELF) technique, has been used to describe chemical bonding in the cluster series Sin(BH)(5-n)(2-) (n = 0-5). The method combines the chemically intuitive information obtained from the traditional ELF analysis with the flexibility and generality of canonical molecular orbital theory. This procedure attempts to localize the molecular orbitals in regions that have the highest probability for finding a pair of electrons, providing a chemical bonding description according to the classical Lewis theory. The results confirm that conservation of the structures upon isoelectronic replacement of a B-H group by a Si atom, allowing evolution from B5H5(2-) to Si5(2-), is in total agreement with the preservation of the chemical bonding pattern.

  19. A Gendered Approach to Understanding the Roles of Social Bonding, Personal Control, and Strain on College Dating Violence in Emerging Adulthood.

    Science.gov (United States)

    Paat, Yok-Fong; Markham, Christine

    2016-01-01

    Borrowing insights from concepts that have been shown to predict deviant or criminal outcomes (i.e., social bonding, personal control, and strain), this study examined dating violence from the perpetrators' and gender-relevance perspective among young college students (18-25 years old). This study raised 2 research questions: Were social bonding, personal control, and strain associated with college dating violence? How did these associations differ by gender? In sum, 2 types of social bonding (commitment to goal attainment and spending time with delinquent peers) were linked to psychological aggression in dating. Whereas self-control was negatively related to dating violence perpetration, antisocial tendencies were associated with physical aggression. Further, all the strain measures (i.e., daily hassles, relationship distress, and couple conflict) had a positive association with dating violence. When gender was considered, self-control had a protective effect for women and antisocial tendencies served as a risk factor for increased psychological violence among men.

  20. Wire bonding in microelectronics

    CERN Document Server

    Harman, George G

    2010-01-01

    Wire Bonding in Microelectronics, Third Edition, has been thoroughly revised to help you meet the challenges of today's small-scale and fine-pitch microelectronics. This authoritative guide covers every aspect of designing, manufacturing, and evaluating wire bonds engineered with cutting-edge techniques. In addition to gaining a full grasp of bonding technology, you'll learn how to create reliable bonds at exceedingly high yields, test wire bonds, solve common bonding problems, implement molecular cleaning methods, and much more. Coverage includes: Ultrasonic bonding systems and technologies, including high-frequency systems Bonding wire metallurgy and characteristics, including copper wire Wire bond testing Gold-aluminum intermetallic compounds and other interface reactions Gold and nickel-based bond pad plating materials and problems Cleaning to improve bondability and reliability Mechanical problems in wire bonding High-yield, fine-pitch, specialized-looping, soft-substrate, and extreme-temperature wire bo...

  1. Graphene composites containing chemically bonded metal oxides

    Indian Academy of Sciences (India)

    (figure 7). We have also been able to bond Al2O3 to graphene by using AlCl3 as the reactant. The oxide film was amor- phous after calcination at 600. ◦. C. We have prepared chemically bonded magnetic Fe3O4 nanoparticles to graphene by functionalizing Fe3O4 by amine, then reacting it with graphene functionalized with.

  2. An Approach for Integrating the Prioritization of Functional and Nonfunctional Requirements

    Directory of Open Access Journals (Sweden)

    Mohammad Dabbagh

    2014-01-01

    Full Text Available Due to the budgetary deadlines and time to market constraints, it is essential to prioritize software requirements. The outcome of requirements prioritization is an ordering of requirements which need to be considered first during the software development process. To achieve a high quality software system, both functional and nonfunctional requirements must be taken into consideration during the prioritization process. Although several requirements prioritization methods have been proposed so far, no particular method or approach is presented to consider both functional and nonfunctional requirements during the prioritization stage. In this paper, we propose an approach which aims to integrate the process of prioritizing functional and nonfunctional requirements. The outcome of applying the proposed approach produces two separate prioritized lists of functional and non-functional requirements. The effectiveness of the proposed approach has been evaluated through an empirical experiment aimed at comparing the approach with the two state-of-the-art-based approaches, analytic hierarchy process (AHP and hybrid assessment method (HAM. Results show that our proposed approach outperforms AHP and HAM in terms of actual time-consumption while preserving the quality of the results obtained by our proposed approach at a high level of agreement in comparison with the results produced by the other two approaches.

  3. Optimal Investment in Structured Bonds

    DEFF Research Database (Denmark)

    Jessen, Pernille; Jørgensen, Peter Løchte

    2012-01-01

    of the article is to provide possible explanations for the puzzle of why small retail investors hold structured bonds. The investment universe consists of a stock index, a risk-free bank account, and a structured bond containing an option written on another index. We apply expected utility maximization......Retail structured products regularly receive much criticism from financial experts but seem to remain popular with investors. This article considers a generic structured product: the principal-protected index-linked note (structured bond), which resembles a portfolio insurance contract. The purpose...... and consider different utility functions and trading strategies. Our results show that investors should include structured bonds in their optimal portfolio only if they cannot access the index underlying the option directly and only if the products then provide sufficient diversification to compensate...

  4. Eshelby-Mori-Tanaka approach for vibrational behavior of functionally graded carbon nanotube-reinforced plate resting on elastic foundation

    Energy Technology Data Exchange (ETDEWEB)

    Kamarian, S.; Pourasghar, A. [Islamic Azad University, Kermanshah (Iran, Islamic Republic of); Yas, M. H. [Razi University, Kermanshah (Iran, Islamic Republic of)

    2013-11-15

    In this study, based on the three-dimensional theory of elasticity, free vibration characteristics of functionally graded (FG) nanocomposite plates reinforced by randomly-oriented straight single-walled carbon nanotubes (SWCNTs) resting on an elastic foundation are considered. Material properties are graded in the thickness direction of the plate according to the volume fraction power law distribution. An embedded carbon nanotube (CNT) in a polymer matrix and its surrounding inter-phase which is perfectly bonded to surrounding resin is replaced with an equivalent fiber to predict the mechanical properties of the carbon nanotube/polymer composite. The Mori-Tanaka approach is employed to calculate the effective elastic moduli of the plate. The natural frequencies of the plate are obtained by means of the generalized differential quadrature (GDQ) method. Detailed parametric studies have been carried out to investigate the influences of the CNT volume fraction, Winkler foundation modulus, shear elastic foundation modulus and various geometrical parameters on the vibration behavior of the functionally graded carbon nanotube-reinforced (FG-CNTR) plates.

  5. Using a Multi-Trait Approach to Manipulate Plant Functional Diversity in a Biodiversity-Ecosystem Function Experiment

    Science.gov (United States)

    Schittko, Conrad; Hawa, Mahmoud; Wurst, Susanne

    2014-01-01

    A frequent pattern emerging from biodiversity-ecosystem function studies is that functional group richness enhances ecosystem functions such as primary productivity. However, the manipulation of functional group richness goes along with major disadvantages like the transformation of functional trait data into categories or the exclusion of functional differences between organisms in the same group. In a mesocosm study we manipulated plant functional diversity based on the multi-trait Functional Diversity (FD)-approach of Petchey and Gaston by using database data of seven functional traits and information on the origin of the species in terms of being native or exotic. Along a gradient ranging from low to high FD we planted 40 randomly selected eight-species mixtures under controlled conditions. We found a significant positive linear correlation of FD with aboveground productivity and a negative correlation with invasibility of the plant communities. Based on community-weighted mean calculations for each functional trait, we figured out that the traits N-fixation and species origin, i.e. being native or exotic, played the most important role for community productivity. Our results suggest that the identification of the impact of functional trait diversity and the relative contributions of relevant traits is essential for a mechanistic understanding of the role of biodiversity for ecosystem functions such as aboveground biomass production and resistance against invasion. PMID:24897501

  6. Approaching human performance the functionality-driven Awiwi robot hand

    CERN Document Server

    Grebenstein, Markus

    2014-01-01

    Humanoid robotics have made remarkable progress since the dawn of robotics. So why don't we have humanoid robot assistants in day-to-day life yet? This book analyzes the keys to building a successful humanoid robot for field robotics, where collisions become an unavoidable part of the game. The author argues that the design goal should be real anthropomorphism, as opposed to mere human-like appearance. He deduces three major characteristics to aim for when designing a humanoid robot, particularly robot hands: _ Robustness against impacts _ Fast dynamics _ Human-like grasping and manipulation performance   Instead of blindly copying human anatomy, this book opts for a holistic design me-tho-do-lo-gy. It analyzes human hands and existing robot hands to elucidate the important functionalities that are the building blocks toward these necessary characteristics.They are the keys to designing an anthropomorphic robot hand, as illustrated in the high performance anthropomorphic Awiwi Hand presented in this book.  ...

  7. A primary care approach to functional abdominal pain.

    Science.gov (United States)

    Scholl, Jennifer; Allen, Patricia Jackson

    2007-01-01

    This article reviews the literature related to functional abdominal pain (FAP) in childhood, including the definition, etiology, contributing factors, clinical diagnosis, therapy and management, and associated long-term health effects. FAP is determined when no specific structural, infectious, inflammatory, or biochemical cause can be found in a child with chronic pain. The presence of abdominal pain as an isolated symptom is more suggestive of FAP, whereas multiple symptoms are more likely to be due to an organic or biochemical condition. While the exact cause of FAP is not completely understood, most researchers and clinicians agree that it is of multi-factorial etiology coupled with an altered brain-gut interaction. Children are highly susceptible to influences around them and can experience pain in response to normal childhood feelings and experiences. Psychological disorders such as anxiety and depression are common in both children with FAP and their parents. Children with FAP tend to have low levels of self-directedness, internalize their feelings and worries, and ruminate over issues they cannot control. The biopsychosocial model has proved to be a worthwhile framework for children with FAP, as it recognizes the interaction between social and environmental influences, psychological processes, and the state of the body. Interventions that focus on the child's cognitive processes associated with abdominal pain and the family's response to the pain have increased efficacy over standard education and reassurance. Providing children and families with techniques to use when experiencing pain decreases alterations in normal daily activities and improves long-term health outcomes.

  8. Holistic approach to functional constipation: Perspective of traditional Persian medicine.

    Science.gov (United States)

    Nimrouzi, Majid; Zarshenas, Mohammad M

    2015-11-23

    Traditional Persian medicine (TPM) proposes a different viewpoint to the chronic diseases. Diagnosis and implemented treatment are based on individual differences among patients. Constipation or Ea'teghal-e-batn is a condition in which the patient develops difficult or painful defecation. Based on TPM concepts, the fifirst digestion step starts from halq (oral cavity), and ends via defecation from the maq'ad (anus). Avicenna believed that four faculties, ha'zemeh (digestive), ja'zebeh (absorptive), ma'sekeh (retentive) and da'fe'eh (propulsive), are involved in the process of digestion and absorption of the ingested food and expelling the waste materials. The bowel movement and appearance of the stool is a measure for evaluating the gastrointestinal healthy function. Defecation should be with no pain and fecal material should have no burning and acuity. Low food intake or foods with dry temperament, dryness of gastrointestinal tract, diaphoresis and heavy exercise as well as intestine sensory loss were discussed as main causes of constipation. Management of constipation in TPM includes dietary schemes, oil massages and subsequently simple herbal medicines. According to TPM theories, the fifirst step in treating a disease is the elimination of disease causes (asbabe- maraz) and also providing the causes of health (asbab-e-sehhat). Health care providers should know the proper condition which the herbal medicines should be administered in and be able to guide the patients about the benefifits and hazards of herbal remedies, commonly used in their living origin.

  9. Systematic Approach toward the Clinical Diagnosis of Functional Dyspepsia

    Directory of Open Access Journals (Sweden)

    Pierre Paré

    1999-01-01

    Full Text Available Functional dyspepsia (FD is the most common condition in patients consulting with upper gastrointestinal tract symptoms, resulting in up to 5% of visits to family physicians. By definition, patients with FD have no clinical, biochemical or endoscopic evidence of an organic disease that is likely to explain their symptoms. The process to be used in a structured interview for establishing a clinical diagnosis of FD is presented. The steps are as follows: determine the duration and the course of the disease; characterize the current syndrome and review the alarm symptoms; elicit the patient-perceived dominant symptom and/or condition; and identify the patient’s reason for consulting and address the psychosocial factors. According to the clinical characteristics of the three most frequent causes of dyspepsia (peptic ulcer, gastroesophageal reflux and FD and acknowledging that these conditions may coexist rather than overlap in some patients, an algorithm is suggested for establishing a working diagnosis of FD and indications for investigation, and initiating a management strategy.

  10. Functional dyspepsia: A new approach from traditional Persian medicine

    Directory of Open Access Journals (Sweden)

    Mehdi Pasalar

    2016-03-01

    Full Text Available Objective: One of the most common global disorders is related to gastrointestinal system. Functional dyspepsia (FD defined as upper abdominal pain and discomfort in the absence of organic ailments is a prevalent disease without any confirmed medication. The purpose of this study was to find gastric disorders which might be coincidental to FD based on traditional Persian medicine (TPM. Materials and Methods: We searched the main textbooks of TPM including Al-Havi (by Rhazes, Canon of medicine (by Avicenna, ZakhireKhawrazmshahi (by Ismail Jorjani, Moalijat-e Aghili and Makhzan Al-adviya (by Mohammad Hosein AghiliShirazi, and ExirAzam (by Hakim Azam Khan. Also, we searched Pubmed, Scopus, Science Direct, Medline, scientific information database (SID, Iranmedex and Google Scholar from 1980 to 1 August 2014 for dyspepsia, gastrointestinal disease, traditional Persian medicine, and gastric dystemperaments. Results: There is no equivalent term for FD in traditional Persian medicine although similar signs and symptoms are visible in terms like simple cold dystemperament of stomach, indigestion, and digestion debility in TPM sources. Some treatments mentioned in TPM have shown promising results in the current experimental tests. Conclusion: Finding these similarities in complementary and alternative medicine (CAM textbooks may lead to discovering new remedies for this widespread disease.

  11. Bond length and electric current oscillation of long linear carbon chains: Density functional theory, MpB model, and quantum spin transport studies

    International Nuclear Information System (INIS)

    Oeiras, R. Y.; Silva, E. Z. da

    2014-01-01

    Carbon linear atomic chains attached to graphene have experimentally been produced. Motivated by these results, we study the nature of the carbon bonds in these nanowires and how it affects their electrical properties. In the present study we investigate chains with different numbers of atoms and we observe that nanowires with odd number of atoms present a distinct behavior than the ones with even numbers. Using graphene nanoribbons as leads, we identify differences in the quantum transport of the chains with the consequence that even and odd numbered chains have low and high electrical conduction, respectively. We also noted a dependence of current with the wire size. We study this unexpected behavior using a combination of first principles calculations and simple models based on chemical bond theory. From our studies, the electrons of carbon nanowires present a quasi-free electron behavior and this explains qualitatively the high electrical conduction and the bond lengths with unexpected values for the case of odd nanowires. Our study also allows the understanding of the electric conduction dependence with the number of atoms and their parity in the chain. In the case of odd number chains a proposed π-bond (MpB) model describes unsaturated carbons that introduce a mobile π-bond that changes dramatically the structure and transport properties of these wires. Our results indicate that the nature of bonds plays the main role in the oscillation of quantum electrical conduction for chains with even and odd number of atoms and also that nanowires bonded to graphene nanoribbons behave as a quasi-free electron system, suggesting that this behavior is general and it could also remain if the chains are bonded to other materials

  12. New Methods of Esterification of Nanodiamonds in Fighting Breast Cancer-A Density Functional Theory Approach.

    Science.gov (United States)

    Landeros-Martinez, Linda-Lucila; Glossman-Mitnik, Daniel; Orrantia-Borunda, Erasmo; Flores-Holguín, Norma

    2017-10-19

    The use of nanodiamonds as anticancer drug delivery vehicles has received much attention in recent years. In this theoretical paper, we propose using different esterification methods for nanodiamonds. The monomers proposed are 2-hydroxypropanal, polyethylene glycol, and polyglicolic acid. Specifically, the hydrogen bonds, infrared (IR) spectra, molecular polar surface area, and reactivity parameters are analyzed. The monomers proposed for use in esterification follow Lipinski's rule of five, meaning permeability is good, they have good permeation, and their bioactivity is high. The results show that the complex formed between tamoxifen and nanodiamond esterified with polyglicolic acid presents the greatest number of hydrogen bonds and a good amount of molecular polar surface area. Calculations concerning the esterified nanodiamond and reactivity parameters were performed using Density Functional Theory with the M06 functional and the basis set 6-31G (d); for the esterified nanodiamond-Tamoxifen complexes, the semi-empirical method PM6 was used. The solvent effect has been taken into account by using implicit modelling and the conductor-like polarizable continuum model.

  13. New Methods of Esterification of Nanodiamonds in Fighting Breast Cancer—A Density Functional Theory Approach

    Directory of Open Access Journals (Sweden)

    Linda-Lucila Landeros-Martinez

    2017-10-01

    Full Text Available The use of nanodiamonds as anticancer drug delivery vehicles has received much attention in recent years. In this theoretical paper, we propose using different esterification methods for nanodiamonds. The monomers proposed are 2-hydroxypropanal, polyethylene glycol, and polyglicolic acid. Specifically, the hydrogen bonds, infrared (IR spectra, molecular polar surface area, and reactivity parameters are analyzed. The monomers proposed for use in esterification follow Lipinski’s rule of five, meaning permeability is good, they have good permeation, and their bioactivity is high. The results show that the complex formed between tamoxifen and nanodiamond esterified with polyglicolic acid presents the greatest number of hydrogen bonds and a good amount of molecular polar surface area. Calculations concerning the esterified nanodiamond and reactivity parameters were performed using Density Functional Theory with the M06 functional and the basis set 6–31G (d; for the esterified nanodiamond–Tamoxifen complexes, the semi-empirical method PM6 was used. The solvent effect has been taken into account by using implicit modelling and the conductor-like polarizable continuum model.

  14. Generalized generating functional for mixed-representation Green's functions: A quantum-mechanical approach

    Science.gov (United States)

    Blasone, Massimo; Jizba, Petr; Smaldone, Luca

    2017-11-01

    When one tries to take into account the nontrivial vacuum structure of quantum field theory, the standard functional-integral tools, such as generating functionals or transitional amplitudes, are often quite inadequate for such purposes. Here we propose a generalized generating functional for Green's functions which allows one to easily distinguish among a continuous set of vacua that are mutually connected via unitary canonical transformations. In order to keep our discussion as simple as possible, we limit ourselves to quantum mechanics where the generating functional of Green's functions is constructed by means of phase-space path integrals. The quantum-mechanical setting allows us to accentuate the main logical steps involved without embarking on technical complications such as renormalization or inequivalent representations that should otherwise be addressed in the full-fledged quantum field theory. We illustrate the inner workings of the generating functional obtained by discussing Green's functions among vacua that are mutually connected via translations and dilatations. Salient issues, including connection with quantum field theory, vacuum-to-vacuum transition amplitudes, and perturbation expansion in the vacuum parameter, are also briefly discussed.

  15. A Geometric Approach to Decouple Robotino Motions and its Functional Controllability

    OpenAIRE

    Straßberger, Daniel; Mercorelli, Paolo; Sergiyenko, Oleg Yu

    2015-01-01

    This paper analyses a functional control of the Robotino. The proposed controlstrategy considers a functional decoupling control strategy realized using a geometric Approach and the invertibility property of the DC-drives with which the Robotino is equipped. For a given control structure the functional controllability is proven for motion trajectories of class C^3, continuous functions with third derivative also being continuous. Horizontal, Vertical andAngular motions are considered and the ...

  16. Native defects in oxide semiconductors: a density functional approach.

    Science.gov (United States)

    Oba, Fumiyasu; Choi, Minseok; Togo, Atsushi; Seko, Atsuto; Tanaka, Isao

    2010-09-29

    We report a semilocal and hybrid Hartree-Fock density functional study of native defects in three oxide semiconductors: ZnO, SrTiO(3), and SnO. The defect that is responsible for the n-type conductivity of ZnO has been debated, in which the O vacancy, Zn interstitial, their complexes, and residual H impurity are considered candidates. Our results indicate that the O vacancy induces a deep and localized in-gap state, whereas the Zn interstitial is a shallow donor and hence can be a source of the carriers. In view of the formation energies, the O vacancy is likely to form with a substantial concentration under O-poor conditions, but the Zn interstitial is unlikely. We thus propose that the O vacancy is relevant to the nonstoichiometry of ZnO and that a source other than the native defects, such as the H impurity, needs to be considered for the n-type conductivity. For SrTiO(3), the O vacancy and its complexes have been regarded as the origins of some of the remarkable electrical and optical properties. We suggest significant roles of the Ti antisite for a new insight into the defect-induced properties. Two types of Ti antisite, both of which are off-centered from the Sr site but toward different directions, exhibit low formation energies under Ti-rich conditions as does the O vacancy. They can explain optical properties such as visible-light emission, deep-level absorption, and the ferroelectricity observed in reduced SrTiO(3). As an example of p-type conductors, SnO has been investigated with a focus on the acceptor-like native defects. Under O-rich conditions, the Sn vacancy and O interstitial are found to be energetically favorable. The Sn vacancy induces shallow acceptor levels and can therefore be a source of carriers. The O interstitial shows no in-gap levels and hence it is inactive in terms of the carrier generation and compensation. However, this defect is a key to the understanding of the structures of intermediate compounds between SnO and SnO(2).

  17. Discovery of molluscicidal and cercaricidal activities of 3-substituted quinazolinone derivatives by a scaffold hopping approach using a pseudo-ring based on the intramolecular hydrogen bond formation.

    Science.gov (United States)

    Guo, Wei; Zheng, Lv-Yin; Li, Yong-Dong; Wu, Ren-Miao; Chen, Qiang; Yang, Ding-Qiao; Fan, Xiao-Lin

    2016-06-10

    Discovery of novel topological agents against Oncomelania hupensis snails and cercariae remains a significant challenge in current Schistosomiasis control. A pseudo-ring formed from salicylanilide by an intramolecular hydrogen bond led to the discovery of 3-substituted quinazolinone derivatives which showed a potent molluscicidal and cercaricidal activities. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

  18. A novel approach for a C-11C bond formation: synthesis of 17α-([11C]prop-1-ynyl)-3-methoxy-3,17β-estradiol

    International Nuclear Information System (INIS)

    Wuest, F.; Zessin, J.

    2002-01-01

    A novel method for a 11 C-C bond formation was developed, employing a cross-coupling reaction between a terminal acetylene and [ 11 C]methyl iodide. The method was used for the synthesis of 17α-([ 11 C]prop-1-ynyl)-3-methoxy-3,17β-estadiol. (orig.)

  19. X hydrogen bonds

    Indian Academy of Sciences (India)

    sigma electrons, can be hydrogen bond acceptors.11–14. The recent IUPAC report and recommendation on hydro gen bond have recognised the diverse nature of hydro- gen bond donors and acceptors.13,14. Unlike methane, hydrogen bonding by higher alkanes has not received much attention. One of the earlier works.

  20. ANALYTIC CAUSATIVES IN JAVANESE: A LEXICAL- FUNCTIONAL APPROACH

    Directory of Open Access Journals (Sweden)

    Agus Subiyanto

    2014-01-01

    Full Text Available Analytic  causatives  are  the  type  of  causatives  formed  by  separate predicates  expressing the cause and the effect, that is, the causing notion  is  realized  by  a  word  separate  from  the  word  denoting  the caused activity. This paper aims to discuss the forms and syntactic structure  of  analytic  causatives  in  Javanese.  To  discuss  the syntactic structure, the theory of lexical functional grammar (LFG is  employed.  The  data  used  in  this  study  is  the  „ngoko‟  level  of Javanese of the Surakarta dialect. By using a negation marker and modals  as  the  syntactic  operators to test mono-  or bi-clausality  of analytic  causatives,  the  writer  found  that  analytic  causatives  in Javanese form biclausal constructions. These constructions have an X-COMP  structure,  in  that  the  SUBJ  of  the  second  verb  is controlled  by  the  OBJ  of  the  causative  verb  (Ngawe  „make‟.  In terms  of  the  constituent  structure,  analytic  causatives  have  two kinds of structures, which are V-cause OBJ X-COMP and V-cause X-COMP OBJ. Kausatif  analitik  adalah  tipe  kausatif  yang  dibentuk  oleh  dua predikat  atau  dua  kata  terpisah  untuk  mengungkapkan  makna sebab dan akibat, yakni makna sebab direalisasikan oleh kata yang berbeda  dengan  kata  yang  menyatakan  makna  akibat.  Tulisan  ini membahas  bentuk  dan  struktur  sintaksis  kausatif  analitik  dalam bahasa Jawa. Untuk menjelaskan struktur sintaksis digunakan teori Tata  Bahasa  Leksikal  Fungsional.  Data  yang  digunakan  dalam penelitian  ini  adalah  bahasa  Jawa  dialek  Surakarta  ragam  ngoko. Dengan  menggunakan  alat  uji  pemarkah  negasi  dan  penggunaaan modalitas,  penulis  menemukan  bahwa  kausatif  analitik  dalam bahasa Jawa membentuk struktur biklausa. Konstruksi ini memiliki struktur  X

  1. Adhesive wafer bonding

    Science.gov (United States)

    Niklaus, F.; Stemme, G.; Lu, J.-Q.; Gutmann, R. J.

    2006-02-01

    Wafer bonding with intermediate polymer adhesives is an important fabrication technique for advanced microelectronic and microelectromechanical systems, such as three-dimensional integrated circuits, advanced packaging, and microfluidics. In adhesive wafer bonding, the polymer adhesive bears the forces involved to hold the surfaces together. The main advantages of adhesive wafer bonding include the insensitivity to surface topography, the low bonding temperatures, the compatibility with standard integrated circuit wafer processing, and the ability to join different types of wafers. Compared to alternative wafer bonding techniques, adhesive wafer bonding is simple, robust, and low cost. This article reviews the state-of-the-art polymer adhesive wafer bonding technologies, materials, and applications.

  2. LAMMPS Framework for Dynamic Bonding and an Application Modeling DNA

    DEFF Research Database (Denmark)

    Svaneborg, Carsten

    2012-01-01

    and bond types. When breaking bonds, all angular and dihedral interactions involving broken bonds are removed. The framework allows chemical reactions to be modeled, and use it to simulate a simplistic, coarse-grained DNA model. The resulting DNA dynamics illustrates the power of the present framework.......We have extended the Large-scale Atomic/Molecular Massively Parallel Simulator (LAMMPS) to support directional bonds and dynamic bonding. The framework supports stochastic formation of new bonds, breakage of existing bonds, and conversion between bond types. Bond formation can be controlled...... to limit the maximal functionality of a bead with respect to various bond types. Concomitant with the bond dynamics, angular and dihedral interactions are dynamically introduced between newly connected triplets and quartets of beads, where the interaction type is determined from the local pattern of bead...

  3. Emphasizing the Significance of Electrostatic Interactions in Chemical Bonding

    Science.gov (United States)

    Venkataraman, Bhawani

    2017-01-01

    This paper describes a pedagogical approach to help students understand chemical bonding by emphasizing the importance of electrostatic interactions between atoms. The approach draws on prior studies that have indicated many misconceptions among students in understanding the nature of the chemical bond and energetics associated with bond formation…

  4. Bond Graph Modeling and Simulation of Mechatronic Systems

    DEFF Research Database (Denmark)

    Habib, Tufail; Nielsen, Kjeld; Jørgensen, Kaj Asbjørn

    2012-01-01

    One of the demanding steps in the design and development of Mechatronic systems is to develop the initial model to visualize the response of a system. The Bond Graph (BG) method is a graphical approach for the design of multidomain systems. That is ideal for visualizing the essential characterist......One of the demanding steps in the design and development of Mechatronic systems is to develop the initial model to visualize the response of a system. The Bond Graph (BG) method is a graphical approach for the design of multidomain systems. That is ideal for visualizing the essential...... characteristics of a system. This paper explores the BG method as a modeling approach to develop Mechatronic systems; a case study about the Radar Antenna pedestal drive system is comprehensively addressed. Flow of energy between different functional elements of the system and their causalities are analyzed...

  5. Novel Vaccine Approach Achieves “Functional Cure” of AIDS Virus in Monkeys | FNLCR

    Science.gov (United States)

    Scientists at the Oregon Health & Science University and the AIDS and Cancer Virus Program of the Frederick National Laboratory for Cancer Research have used a novel vaccine approach to achieve a “functional cure” and apparent eradication of infe

  6. The Language Laboratory and the Functional Approach: From Pattern Practice to Communication.

    Science.gov (United States)

    Salvi, Rita

    1982-01-01

    The author discusses the reasons for using the language laboratory in foreign language instruction now that the functional approach has replaced the audiolingual method and gives examples of possible lab exercises. (CFM)

  7. Estimated Quality of Multistage Process on the Basis of Probabilistic Approach with Continuous Response Functions

    Directory of Open Access Journals (Sweden)

    Yuri B. Tebekin

    2011-11-01

    Full Text Available The article is devoted to the problem of the quality management for multiphase processes on the basis of the probabilistic approach. Method with continuous response functions is offered from the application of the method of Lagrange multipliers.

  8. A Multireference Density Functional Approach to the Calculation of the Excited States of Uranium Ions

    Science.gov (United States)

    2007-03-01

    oxidation of uranium oxides in molten salts and in the solid state to forum alkali metal uranates, and their composition and properties,” Journal of...AFIT/DS/ENP/07-01 A MULTIREFERENCE DENSITY FUNCTIONAL APPROACH TO THE CALCULATION OF THE EXCITED STATES OF URANIUM IONS DISSERTATION Eric V. Beck...FUNCTIONAL APPROACH TO THE CALCULATION OF THE EXCITED STATES OF URANIUM IONS DISSERTATION Presented to the Faculty of the School of Engineering

  9. A translational approach to the functional analysis of language in psychotherapy

    OpenAIRE

    Javier Virues-Ortega; María Xesús Froján-Parga

    2015-01-01

    The functional analysis of verbal behavior has been successful in establishing basic and advanced forms of language in individuals with developmental disabilities. The development of behavioral approaches to psychotherapy, such as the functional-analytic psychotherapy, have advanced the implementation of operant analyses of verbal behavior among typical adults. The field of behavior-analytic approaches to psychotherapy departs from the applied experimental research in behavior analysis in ...

  10. REQUIREMENTS PARTICLE NETWORKS: AN APPROACH TO FORMAL SOFTWARE FUNCTIONAL REQUIREMENTS MODELLING

    OpenAIRE

    Wiwat Vatanawood; Wanchai Rivepiboon

    2001-01-01

    In this paper, an approach to software functional requirements modelling using requirements particle networks is presented. In our approach, a set of requirements particles is defined as an essential tool to construct a visual model of software functional requirements specification during the software analysis phase and the relevant formal specification is systematically generated without the experience of writing formal specification. A number of algorithms are presented to perform these for...

  11. Power function arguments in support of an alternative approach for analyzing management trials.

    Science.gov (United States)

    Willan, A R

    1994-06-01

    Power function arguments are used in support of an alternative approach for analyzing management trials. Central to the arguments is the recognition that, based on interpreting the smallest clinically important difference as a point of indifference, management trials require different power functions than explanatory trials. This interpretation of the smallest clinically important difference implies a specific ideal power function, and the alternative approach, by testing a nonzero null hypothesis at the appropriate level, is designed to achieve a power function with intuitive appeal and some optimal properties with respect to this ideal function. The alternative approach, by moving away from the traditional null hypothesis, better reflects clinical considerations, and eliminates the conflict between statistical and clinical significance. In addition, with adequate sample size, a decision in favor of the superior treatment will be made with a predetermined high level of confidence, if the therapies differ significantly.

  12. Molecular structure, heteronuclear resonance assisted hydrogen bond analysis, chemical reactivity and first hyperpolarizability of a novel ethyl-4-{[(2,4-dinitrophenyl)-hydrazono]-ethyl}-3,5-dimethyl-1H-pyrrole-2-carboxylate: a combined DFT and AIM approach.

    Science.gov (United States)

    Singh, R N; Kumar, Amit; Tiwari, R K; Rawat, Poonam; Baboo, Vikas; Verma, Divya

    2012-06-15

    A new ethyl-4-{[(2,4-dinitrophenyl)-hydrazono]-ethyl}-3,5-dimethyl-1H-pyrrole-2-carboxylate (EDPHEDPC) has been synthesized and characterized by FT-IR, (1)H NMR, UV-vis, DART-Mass spectroscopy and elemental analysis. Quantum chemical calculations have been performed by DFT level of theory using B3LYP functional and 6-31G(d,p) as basis set. The (1)H NMR chemical shifts are calculated using gauge including atomic orbitals (GIAO) approach in DMSO as solvent. The time dependent density functional theory (TD-DFT) is used to find the various electronic transitions and their nature within molecule. A combined theoretical and experimental wavenumber analysis confirms the existence of dimer. Topological parameters such as electron density (ρ(BCP)), Laplacian of electron density (nabla(2)ρ(BCP)), kinetic electron energy density (G(BCP)), potential electron density (V(BCP)) and the total electron energy density (H(BCP)) at bond critical points (BCP) have been analyzed by Bader's 'Atoms in molecules' AIM theory in detail. The intermolecular hydrogen bond energy of dimer is calculated as -12.51 kcal/mol using AIM calculations. AIM ellipticity analysis is carried out to confirm the presence of resonance assisted intra and intermolecular hydrogen bonds in dimer. The calculated thermodynamic parameters show that reaction is exothermic and non-spontaneous at room temperature. The local reactivity descriptors such as Fukui functions (f(k)(+), f(k)(-)), local softnesses (s(k)(-), s(k)(+)) and electrophilicity indices (ω(k)(+), ω(k)(-)) analyses are performed to determine the reactive sites within molecule. Nonlinear optical (NLO) behavior of title compound is investigated by the computed value of first hyperpolarizability (β(0)). Copyright © 2012 Elsevier B.V. All rights reserved.

  13. Molecular-crystal approach to accounting of correlation corrections in the chemical bond theory in crystals: electronic structure of Ti2O3 crystal

    International Nuclear Information System (INIS)

    Ehvarestov, R.A.; Panin, A.I.

    2000-01-01

    The problem on the possibility of partial accounting for the electron correlation effects within the frames of the Hartree-Fock unlimited method (HF). The local characteristic of the electron structure of the molecular systems for the case of the multi-determinant wave functions, configurational interaction methods and multiconfigurational self-consistent field (MCSCF) are determined. The molecular-crystalline approach is applied to studies on the electron correlation effects in the Ti 2 O 3 crystal. It is shown on the basis of the [Ti 2 O 9 ] 12- cluster electron structure calculation, that the Hartree-Fock unlimited method accounts in a number of cases for an essential part of statistical correlation effects. The energy values and local characteristics of the [Ti 2 O 9 ] 12- cluster, calculated through the HF and MCSCF methods, are presented [ru

  14. A discrimlnant function approach to ecological site classification in northern New England

    Science.gov (United States)

    James M. Fincher; Marie-Louise Smith

    1994-01-01

    Describes one approach to ecologically based classification of upland forest community types of the White and Green Mountain physiographic regions. The classification approach is based on an intensive statistical analysis of the relationship between the communities and soil-site factors. Discriminant functions useful in distinguishing between types based on soil-site...

  15. Detection of Differential Item Functioning with Nonlinear Regression: A Non-IRT Approach Accounting for Guessing

    Science.gov (United States)

    Drabinová, Adéla; Martinková, Patrícia

    2017-01-01

    In this article we present a general approach not relying on item response theory models (non-IRT) to detect differential item functioning (DIF) in dichotomous items with presence of guessing. The proposed nonlinear regression (NLR) procedure for DIF detection is an extension of method based on logistic regression. As a non-IRT approach, NLR can…

  16. Evaluation of the Function and Quality of Life after Total Hip Arthroplasty by Different Approaches

    Directory of Open Access Journals (Sweden)

    Paulo Araújo

    2017-09-01

    Conclusion: After 24 months post total hip arthroplasty there are no differences between the two approaches with regard to function or quality of life. However, the patients operated by the anterolateral approach had greater muscle strength deficits and higher percentage of positive Trendelenburg test.

  17. Points of convergence between functional and formal approaches to syntactic analysis

    DEFF Research Database (Denmark)

    Bjerre, Tavs; Engels, Eva; Jørgensen, Henrik

    2008-01-01

    respectively: The functional approach is represented by Paul Diderichsen's (1936, 1941, 1946, 1964) sætningsskema, ‘sentence model', and the formal approach is represented by analysis whose main features are common to the principles and parameters framework (Chomsky 1986) and the minimalist programme (Chomsky...

  18. Contribution of single-strand breaks and alkali-labile bonds to the loss of infectivity of γ-irradiated phiX174 RF-DNA in E. coli cells mutant in various repair functions

    International Nuclear Information System (INIS)

    McKee, R.H.

    1975-01-01

    Twenty-one radiation sensitive mutants have been examined for their capacity to support gamma-irradiated phiX174 RF-DNA. The survival of phiX174 RF-DNA was reduced in essentially all of the sensitive mutants. The irradiated phiX174 RF-DNA was then separated into populations containing either single-strand breaks or alkali-labile bonds to examine the capacity of the mutants to repair each of the classes of lesions. It was found that all E. coli strains are unable to repair 22 percent of the single-strand breaks and all sensitive mutants are unable to repair an additional 10 percent of the breaks. All the repair functions examined are involved in single-strand break repair and none are more or less necessary than any of the others. PhiX174 RF-DNA is also inactivated by alkali-labile bonds. In the normal strains the inactivation efficiency is 0.16 lethal events per lesion with a threshold dose of 15 to 20 krads. The mutants are divided into two classes by their sensitivity to alkali-labile bonds. Both classes of mutants are also inactivated by alkali-labile bonds with efficiencies of about 0.17 and 0.29 lethal events per lesion, respectively. It is proposed that the differences seen in survival curves of phiX174 measured in the sensitive mutants is due to this difference. Although in normal cells the efficiency of inactivation of phiX174 by single-strand breaks is 50 percent greater than by alkali-labile bonds, alkali-labile bonds are produced at approximately twice the rate of single-strand breaks so alkali-labile bonds account for about 61 percent of the overall inactivation. In the mutants of least sensitivity alkali-labile bonds account for about 54 percent of the inactivating events and in the most sensitive about 67 percent

  19. Nanoparticle/Polymer Nanocomposite Bond Coat or Coating

    Science.gov (United States)

    Miller, Sandi G.

    2011-01-01

    This innovation addresses the problem of coatings (meant to reduce gas permeation) applied to polymer matrix composites spalling off in service due to incompatibility with the polymer matrix. A bond coat/coating has been created that uses chemically functionalized nanoparticles (either clay or graphene) to create a barrier film that bonds well to the matrix resin, and provides an outstanding barrier to gas permeation. There is interest in applying clay nanoparticles as a coating/bond coat to a polymer matrix composite. Often, nanoclays are chemically functionalized with an organic compound intended to facilitate dispersion of the clay in a matrix. That organic modifier generally degrades at the processing temperature of many high-temperature polymers, rendering the clay useless as a nano-additive to high-temperature polymers. However, this innovation includes the use of organic compounds compatible with hightemperature polymer matrix, and is suitable for nanoclay functionalization, the preparation of that clay into a coating/bondcoat for high-temperature polymers, the use of the clay as a coating for composites that do not have a hightemperature requirement, and a comparable approach to the preparation of graphene coatings/bond coats for polymer matrix composites.

  20. A Factor Analytic and Regression Approach to Functional Age: Potential Effects of Race.

    Science.gov (United States)

    Colquitt, Alan L.; And Others

    Factor analysis and multiple regression are two major approaches used to look at functional age, which takes account of the extensive variation in the rate of physiological and psychological maturation throughout life. To examine the role of racial or cultural influences on the measurement of functional age, a battery of 12 tests concentrating on…

  1. A Two Layer Approach to the Computability and Complexity of Real Functions

    DEFF Research Database (Denmark)

    Lambov, Branimir Zdravkov

    2003-01-01

    We present a new model for computability and complexity of real functions together with an implementation that it based on it. The model uses a two-layer approach in which low-type basic objects perform the computation of a real function, but, whenever needed, can be complemented with higher type...

  2. Trait-based approaches for understanding microbial biodiversity and ecosystem functioning

    NARCIS (Netherlands)

    Krause, S.; Le Roux, X.; Niklaus, P.A.; van Bodegom, P.M.; Lennon, J.T.; Bertilsson, S.A.; Grossart, H.P.; Philippot, L.; Bodelier, P.L.E.

    2014-01-01

    In ecology, biodiversity-ecosystem functioning (BEF) research has seen a shift in perspective from taxonomy to function in the last two decades, with successful application of trait-based approaches. This shift offers opportunities for a deeper mechanistic understanding of the role of biodiversity

  3. A Functional-Notional Approach for English for Specific Purposes (ESP) Programs.

    Science.gov (United States)

    Kim, Young-Min

    English for Specific Purposes (ESP) programs, characterized by the special needs of the language learners, are described and a review of the literature on a functional-notional approach to the syllabus design of ESP programs is presented. It is suggested that effective ESP programs should teach the language skills necessary to function and perform…

  4. A Functional Approach to Evaluating Content Knowledge and Language Development in ESL Students' Science Classification Texts.

    Science.gov (United States)

    Huang, Jingzi; Morgan, Glenn

    2003-01-01

    Investigates use of a functional approach to discourse analysis--knowledge structure analysis, which focuses on meaning, form, and function simultaneously--to evaluate both writing development and content learning. Examined written texts in science, produced by English-as-a-Second-Language students with limited to intermediate English language…

  5. Numerical approach of the bond stress behavior of steel bars embedded in self-compacting concrete and in ordinary concrete using beam models

    Directory of Open Access Journals (Sweden)

    F.M. Almeida Filho

    Full Text Available The present study evaluates the bond behavior between steel bars and concrete by means of a numerical analysis based on Finite Element Method. Results of a previously conducted experimental program on reinforced concrete beams subjected to monotonic loading are also presented. Two concrete types, self-compacting concrete and ordinary concrete, were considered in the study. Non-linear constitutive relations were used to represent concrete and steel in the proposed numerical model, aiming to reproduce the bond behavior observed in the tests. Experimental analysis showed similar results for the bond resistances of self-compacting and ordinary concrete, with self-compacting concrete presenting a better performance in some cases. The results given by the numerical modeling showed a good agreement with the tests for both types of concrete, especially in the pre-peak branch of the load vs. slip and load vs. displacement curves. As a consequence, the proposed numerical model could be used to estimate a reliable development length, allowing a possible reduction of the structure costs.

  6. Toward accurate prediction of potential energy surfaces and the spectral density of hydrogen bonded systems

    International Nuclear Information System (INIS)

    Rekik, Najeh

    2014-01-01

    Despite the considerable progress made in quantum theory and computational methods, detailed descriptions of the potential energy surfaces of hydrogen-bonded systems have not yet been achieved. In addition, the hydrogen bond (H-bond) itself is still so poorly understood at the fundamental level that it remains unclear exactly what geometry constitutes a “real” H-bond. Therefore, in order to investigate features essential for hydrogen bonded complexes, a simple, efficient, and general method for calculating matrix elements of vibrational operators capable of describing the stretching modes and the H-bond bridges of hydrogen-bonded systems is proposed. The derived matrix elements are simple and computationally easy to evaluate, which makes the method suitable for vibrational studies of multiple-well potentials. The method is illustrated by obtaining potential energy surfaces for a number of two-dimensional systems with repulsive potentials chosen to be in Gaussian form for the stretching mode and of the Morse-type for the H-bond bridge dynamics. The forms of potential energy surfaces of weak and strong hydrogen bonds are analyzed by varying the asymmetry of the Gaussian potential. Moreover, the choice and applicability of the selected potential for the stretching mode and comparison with other potentials used in the area of hydrogen bond research are discussed. The approach for the determination of spectral density has been constructed in the framework of the linear response theory for which spectral density is obtained by Fourier transform of the autocorrelation function of the dipole moment operator of the fast mode. The approach involves anharmonic coupling between the high frequency stretching vibration (double well potential) and low-frequency donor-acceptor stretching mode (Morse potential) as well as the electrical anharmonicity of the dipole moment operator of the fast mode. A direct relaxation mechanism is incorporated through a time decaying exponential

  7. Killing the Hofstadter butterfly, one bond at a time

    Science.gov (United States)

    Agarwala, Adhip

    2017-01-01

    Electronic bands in a square lattice when subjected to a perpendicular magnetic field form the Hofstadter butterfly pattern. We study the evolution of this pattern as a function of bond percolation disorder (removal or dilution of lattice bonds). With increasing concentration of the bonds removed, the butterfly pattern gets smoothly decimated. However, in this process of decimation, bands develop interesting characteristics and features. For example, in the high disorder limit, some butterfly-like pattern still persists even as most of the states are localized. We also analyze, in the low disorder limit, the effect of percolation on wavefunctions (using inverse participation ratios) and on band gaps in the spectrum. We explain and provide the reasons behind many of the key features in our results by analyzing small clusters and finite size rings. Furthermore, we study the effect of bond dilution on transverse conductivity ( σ xy ). We show that starting from the clean limit, increasing disorder reduces σ xy to zero, even though the strength of percolation is smaller than the classical percolation threshold. This shows that the system undergoes a direct transition from a integer quantum Hall state to a localized Anderson insulator beyond a critical value of bond dilution. We further find that the energy bands close to the band edge are more stable to disorder than at the band center. To arrive at these results we use the coupling matrix approach to calculate Chern numbers for disordered systems. We point out the relevance of these results to signatures in magneto-oscillations.

  8. Integrating community assembly and biodiversity to better understand ecosystem function: the Community Assembly and the Functioning of Ecosystems (CAFE) approach.

    Science.gov (United States)

    Bannar-Martin, Katherine H; Kremer, Colin T; Ernest, S K Morgan; Leibold, Mathew A; Auge, Harald; Chase, Jonathan; Declerck, Steven A J; Eisenhauer, Nico; Harpole, Stanley; Hillebrand, Helmut; Isbell, Forest; Koffel, Thomas; Larsen, Stefano; Narwani, Anita; Petermann, Jana S; Roscher, Christiane; Cabral, Juliano Sarmento; Supp, Sarah R

    2018-02-01

    The research of a generation of ecologists was catalysed by the recognition that the number and identity of species in communities influences the functioning of ecosystems. The relationship between biodiversity and ecosystem functioning (BEF) is most often examined by controlling species richness and randomising community composition. In natural systems, biodiversity changes are often part of a bigger community assembly dynamic. Therefore, focusing on community assembly and the functioning of ecosystems (CAFE), by integrating both species richness and composition through species gains, losses and changes in abundance, will better reveal how community changes affect ecosystem function. We synthesise the BEF and CAFE perspectives using an ecological application of the Price equation, which partitions the contributions of richness and composition to function. Using empirical examples, we show how the CAFE approach reveals important contributions of composition to function. These examples show how changes in species richness and composition driven by environmental perturbations can work in concert or antagonistically to influence ecosystem function. Considering how communities change in an integrative fashion, rather than focusing on one axis of community structure at a time, will improve our ability to anticipate and predict changes in ecosystem function. © 2017 The Authors. Ecology Letters published by CNRS and John Wiley & Sons Ltd.

  9. Approaches to Modelling the Dynamical Activity of Brain Function Based on the Electroencephalogram

    Science.gov (United States)

    Liley, David T. J.; Frascoli, Federico

    The brain is arguably the quintessential complex system as indicated by the patterns of behaviour it produces. Despite many decades of concentrated research efforts, we remain largely ignorant regarding the essential processes that regulate and define its function. While advances in functional neuroimaging have provided welcome windows into the coarse organisation of the neuronal networks that underlie a range of cognitive functions, they have largely ignored the fact that behaviour, and by inference brain function, unfolds dynamically. Modelling the brain's dynamics is therefore a critical step towards understanding the underlying mechanisms of its functioning. To date, models have concentrated on describing the sequential organisation of either abstract mental states (functionalism, hard AI) or the objectively measurable manifestations of the brain's ongoing activity (rCBF, EEG, MEG). While the former types of modelling approach may seem to better characterise brain function, they do so at the expense of not making a definite connection with the actual physical brain. Of the latter, only models of the EEG (or MEG) offer a temporal resolution well matched to the anticipated temporal scales of brain (mental processes) function. This chapter will outline the most pertinent of these modelling approaches, and illustrate, using the electrocortical model of Liley et al, how the detailed application of the methods of nonlinear dynamics and bifurcation theory is central to exploring and characterising their various dynamical features. The rich repertoire of dynamics revealed by such dynamical systems approaches arguably represents a critical step towards an understanding of the complexity of brain function.

  10. A biopsychosocial approach to women's sexual function and dysfunction at midlife: A narrative review.

    Science.gov (United States)

    Thomas, Holly N; Thurston, Rebecca C

    2016-05-01

    A satisfying sex life is an important component of overall well-being, but sexual dysfunction is common, especially in midlife women. The aim of this review is (a) to define sexual function and dysfunction, (b) to present theoretical models of female sexual response, (c) to examine longitudinal studies of how sexual function changes during midlife, and (d) to review treatment options. Four types of female sexual dysfunction are currently recognized: Female Orgasmic Disorder, Female Sexual Interest/Arousal Disorder, Genito-Pelvic Pain/Penetration Disorder, and Substance/Medication-Induced Sexual Dysfunction. However, optimal sexual function transcends the simple absence of dysfunction. A biopsychosocial approach that simultaneously considers physical, psychological, sociocultural, and interpersonal factors is necessary to guide research and clinical care regarding women's sexual function. Most longitudinal studies reveal an association between advancing menopause status and worsening sexual function. Psychosocial variables, such as availability of a partner, relationship quality, and psychological functioning, also play an integral role. Future directions for research should include deepening our understanding of how sexual function changes with aging and developing safe and effective approaches to optimizing women's sexual function with aging. Overall, holistic, biopsychosocial approaches to women's sexual function are necessary to fully understand and treat this key component of midlife women's well-being. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

  11. A biopsychosocial approach to women’s sexual function and dysfunction at midlife: A narrative review

    Science.gov (United States)

    Thomas, Holly N.; Thurston, Rebecca C.

    2016-01-01

    A satisfying sex life is an important component of overall well-being, but sexual dysfunction is common, especially in midlife women. The aim of this review is (a) to define sexual function and dysfunction, (b) to present theoretical models of female sexual response, (c) to examine longitudinal studies of how sexual function changes during midlife, and (d) to review treatment options. Four types of female sexual dysfunction are currently recognized: Female Orgasmic Disorder, Female Sexual Interest/Arousal Disorder, Genito-Pelvic Pain/Penetration Disorder, and Substance/Medication-Induced Sexual Dysfunction. However, optimal sexual function transcends the simple absence of dysfunction. A biopsychosocial approach that simultaneously considers physical, psychological, sociocultural, and interpersonal factors is necessary to guide research and clinical care regarding women’s sexual function. Most longitudinal studies reveal an association between advancing menopause status and worsening sexual function. Psychosocial variables, such as availability of a partner, relationship quality, and psychological functioning, also play an integral role. Future directions for research should include deepening our understanding of how sexual function changes with aging and developing safe and effective approaches to optimizing women’s sexual function with aging. Overall, holistic, biopsychosocial approaches to women’s sexual function are necessary to fully understand and treat this key component of midlife women’s well-being. PMID:27013288

  12. First-principles Green's-function method for surface calculations: A pseudopotential localized basis set approach

    Science.gov (United States)

    Smidstrup, Søren; Stradi, Daniele; Wellendorff, Jess; Khomyakov, Petr A.; Vej-Hansen, Ulrik G.; Lee, Maeng-Eun; Ghosh, Tushar; Jónsson, Elvar; Jónsson, Hannes; Stokbro, Kurt

    2017-11-01

    We present an efficient implementation of a surface Green's-function method for atomistic modeling of surfaces within the framework of density functional theory using a pseudopotential localized basis set approach. In this method, the system is described as a truly semi-infinite solid with a surface region coupled to an electron reservoir, thereby overcoming several fundamental drawbacks of the traditional slab approach. The versatility of the method is demonstrated with several applications to surface physics and chemistry problems that are inherently difficult to address properly with the slab method, including metal work function calculations, band alignment in thin-film semiconductor heterostructures, surface states in metals and topological insulators, and surfaces in external electrical fields. Results obtained with the surface Green's-function method are compared to experimental measurements and slab calculations to demonstrate the accuracy of the approach.

  13. Carbon K-edge X-ray absorption spectroscopy and time-dependent density functional theory examination of metal-carbon bonding in metallocene dichlorides.

    Science.gov (United States)

    Minasian, Stefan G; Keith, Jason M; Batista, Enrique R; Boland, Kevin S; Kozimor, Stosh A; Martin, Richard L; Shuh, David K; Tyliszczak, Tolek; Vernon, Louis J

    2013-10-02

    Metal-carbon covalence in (C5H5)2MCl2 (M = Ti, Zr, Hf) has been evaluated using carbon K-edge X-ray absorption spectroscopy (XAS) as well as ground-state and time-dependent hybrid density functional theory (DFT and TDDFT). Differences in orbital mixing were determined experimentally using transmission XAS of thin crystalline material with a scanning transmission X-ray microscope (STXM). Moving down the periodic table (Ti to Hf) has a marked effect on the experimental transition intensities associated with the low-lying antibonding 1a1* and 1b2* orbitals. The peak intensities, which are directly related to the M-(C5H5) orbital mixing coefficients, increase from 0.08(1) and 0.26(3) for (C5H5)2TiCl2 to 0.31(3) and 0.75(8) for (C5H5)2ZrCl2, and finally to 0.54(5) and 0.83(8) for (C5H5)2HfCl2. The experimental trend toward increased peak intensity for transitions associated with 1a1* and 1b2* orbitals agrees with the calculated TDDFT oscillator strengths [0.10 and 0.21, (C5H5)2TiCl2; 0.21 and 0.73, (C5H5)2ZrCl2; 0.35 and 0.69, (C5H5)2HfCl2] and with the amount of C 2p character obtained from the Mulliken populations for the antibonding 1a1* and 1b2* orbitals [8.2 and 23.4%, (C5H5)2TiCl2; 15.3 and 39.7%, (C5H5)2ZrCl2; 20.1 and 50.9%, (C5H5)2HfCl2]. The excellent agreement between experiment, theory, and recent Cl K-edge XAS and DFT measurements shows that C 2p orbital mixing is enhanced for the diffuse Hf (5d) and Zr (4d) atomic orbitals in relation to the more localized Ti (3d) orbitals. These results provide insight into how changes in M-Cl orbital mixing within the metallocene wedge are correlated with periodic trends in covalent bonding between the metal and the cyclopentadienide ancillary ligands.

  14. Efficient evaluation of dielectric response functions and calculations of ground and excited state properties beyond local Density Functional approaches

    Science.gov (United States)

    Lu, Deyu; Li, Yan; Rocca, Dario; Viet Nguyen, H.; Gygi, Francois; Galli, Giulia

    2010-03-01

    A recently developed technique to diagonalize iteratively dielectric matrices [1], is used to carry out efficient, ab-initio calculations of dispersion interactions, and excited state properties of nanostructures. In particular, we present results for the binding energies of weakly bonded molecular crystals [2], obtained at the EXX/RPA level of theory, and for absorption spectra of semiconducting clusters, obtained by an iterative solution of the Bethe-Salpeter equations [3]. We show that the ability to obtain the eigenmodes of dielectric matrices from Density Functional perturbation theory, without computing single particle excited states, greatly improves the efficiency of both EXX/RPA and many body perturbation theory [3,4] calculations and opens the way to large scale computations. [1] H. Wilson, F. Gygi and G. Galli, Phys. Rev. B , 78, 113303, 2008; and H. Wilson, D. Lu, F. Gygi and G. Galli, Phys. Rev. B, 79, 245106, 2009. [2] D. Lu, Y. Li, D. Rocca and G. Galli, Phys. Rev. Lett, 102, 206411, 2009; and Y. Li, D. Lu, V. Nguyen and G. Galli, J. Phys. Chem. C (submitted) [3] D. Rocca, D. Lu and G. Galli, submitted. [4] D. Lu, F. Gygi and G. Galli, Phys. Rev. Lett. 100, 147601, 2008. Work was funded by DOE/Scidac DE-FC02-06ER25794 and DOE/BES DE-FG02-06ER46262.

  15. A broken-symmetry density functional study of structures, energies, and protonation states along the catalytic O-O bond cleavage pathway in ba3 cytochrome c oxidase from Thermus thermophilus.

    Science.gov (United States)

    Han Du, Wen-Ge; Götz, Andreas W; Yang, Longhua; Walker, Ross C; Noodleman, Louis

    2016-08-21

    Broken-symmetry density functional calculations have been performed on the [Fea3, CuB] dinuclear center (DNC) of ba3 cytochrome c oxidase from Thermus thermophilus in the states of [Fea3(3+)-(HO2)(-)-CuB(2+), Tyr237(-)] and [Fea3(4+)[double bond, length as m-dash]O(2-), OH(-)-CuB(2+), Tyr237˙], using both PW91-D3 and OLYP-D3 functionals. Tyr237 is a special tyrosine cross-linked to His233, a ligand of CuB. The calculations have shown that the DNC in these states strongly favors the protonation of His376, which is above propionate-A, but not of the carboxylate group of propionate-A. The energies of the structures obtained by constrained geometry optimizations along the O-O bond cleavage pathway between [Fea3(3+)-(O-OH)(-)-CuB(2+), Tyr237(-)] and [Fea3(4+)[double bond, length as m-dash]O(2-)HO(-)-CuB(2+), Tyr237˙] have also been calculated. The transition of [Fea3(3+)-(O-OH)(-)-CuB(2+), Tyr237(-)] → [Fea3(4+)[double bond, length as m-dash]O(2-)HO(-)-CuB(2+), Tyr237˙] shows a very small barrier, which is less than 3.0/2.0 kcal mol(-1) in PW91-D3/OLYP-D3 calculations. The protonation state of His376 does not affect this O-O cleavage barrier. The rate limiting step of the transition from state A (in which O2 binds to Fea3(2+)) to state PM ([Fea3(4+)[double bond, length as m-dash]O(2-), OH(-)-CuB(2+), Tyr237˙], where the O-O bond is cleaved) in the catalytic cycle is, therefore, the proton transfer originating from Tyr237 to O-O to form the hydroperoxo [Fea3(3+)-(O-OH)(-)-CuB(2+), Tyr237(-)] state. The importance of His376 in proton uptake and the function of propionate-A/neutral-Asp372 as a gate to prevent the proton from back-flowing to the DNC are also shown.

  16. An Integrated Approach for Non-Recursive Formulation of Connection-Coefficients of Orthogonal Functions

    Directory of Open Access Journals (Sweden)

    Monika GARG

    2012-08-01

    Full Text Available In this paper, an integrated approach is proposed for non-recursive formulation of connection coefficients of different orthogonal functions in terms of a generic orthogonal function. The application of these coefficients arises when the product of two orthogonal basis functions are to be expressed in terms of single basis functions. Two significant advantages are achieved; one, the non-recursive formulations avoid memory and stack overflows in computer implementations; two, the integrated approach provides for digital hardware once-designed can be used for different functions. Computational savings achieved with the proposed non-recursive formulation vis-à-vis recursive formulation, reported in the literature so far, have been demonstrated using MATLAB PROFILER.

  17. A New Approach for Predicting the Variance of Random Decrement Functions

    DEFF Research Database (Denmark)

    Asmussen, J. C.; Brincker, Rune

    mean Gaussian distributed processes the RD functions are proportional to the correlation functions of the processes. If a linear structur is loaded by Gaussian white noise the modal parameters can be extracted from the correlation funtions of the response, only. One of the weaknesses of the RD...... technique is that no consistent approach to estimate the variance of the RD functions is known. Only approximate relations are available, which can only be used under special conditions. The variance of teh RD functions contains valuable information about accuracy of the estimates. Furthermore, the variance...... can be used as basis for a decision about how many time lags from the RD funtions should be used in the modal parameter extraction procedure. This paper suggests a new method for estimating the variance of the RD functions. The method is consistent in the sense that the accuracy of the approach...

  18. A New Approach for Predicting the Variance of Random Decrement Functions

    DEFF Research Database (Denmark)

    Asmussen, J. C.; Brincker, Rune

    1998-01-01

    mean Gaussian distributed processes the RD functions are proportional to the correlation functions of the processes. If a linear structur is loaded by Gaussian white noise the modal parameters can be extracted from the correlation funtions of the response, only. One of the weaknesses of the RD...... technique is that no consistent approach to estimate the variance of the RD functions is known. Only approximate relations are available, which can only be used under special conditions. The variance of teh RD functions contains valuable information about accuracy of the estimates. Furthermore, the variance...... can be used as basis for a decision about how many time lags from the RD funtions should be used in the modal parameter extraction procedure. This paper suggests a new method for estimating the variance of the RD functions. The method is consistent in the sense that the accuracy of the approach...

  19. Grism manufacturing by low temperature mineral bonding

    Science.gov (United States)

    Kalkowski, G.; Grabowski, K.; Harnisch, G.; Flügel-Paul, T.; Zeitner, U.; Risse, S.

    2017-09-01

    By uniting a grating with a prism to a GRISM compound, the optical characteristics of diffractive and refractive elements can be favorably combined to achieve outstanding spectral resolution features. Ruling the grating structure into the prism surface is common for wavelengths around 1 μm and beyond, while adhesive bonding of two separate parts is generally used for shorter wavelengths and finer structures. We report on a manufacturing approach for joining the corresponding glass elements by the technology of hydrophilic direct bonding. This allows to manufacture the individual parts separately and subsequently combine them quasimonolithically by generating stiff and durable bonds of vanishing thickness, high strength and excellent transmission. With this approach for GRISM bonding, standard direct-write- or mask-lithography equipment may be used for the fabrication of the grating structure and the drawbacks of adhesive bonding (thermal mismatch, creep, aging) are avoided. The technology of hydrophilic bonding originates from "classical" optical contacting [1], but has been much improved and perfected during the last decades in the context of 3-dimensinal stacking Si-wafers for microelectronic applications [2]. It provides joins through covalent bonds of the Si-O-Si type at the nanometer scale, i.e. the elementary bond type in many minerals and glasses. The mineral nature of the bond is perfectly adapted to most optical materials and the extremely thin bonding layers generated with this technology are well suited for transmission optics. Creeping under mechanical load, as commonly observed with adhesive bonding, is not an issue. With respect to diffusion bonding, which operates at rather high temperatures close to the glass transition or crystal melting point, hydrophilic bonding is a low temperature process that needs only moderate heating. This facilitates provision of handling and alignment means for the individual parts during the set-up stages and greatly

  20. Mechatronic modeling and simulation using bond graphs

    CERN Document Server

    Das, Shuvra

    2009-01-01

    Introduction to Mechatronics and System ModelingWhat Is Mechatronics?What Is a System and Why Model Systems?Mathematical Modeling Techniques Used in PracticeSoftwareBond Graphs: What Are They?Engineering SystemsPortsGeneralized VariablesBond GraphsBasic Components in SystemsA Brief Note about Bond Graph Power DirectionsSummary of Bond Direction RulesDrawing Bond Graphs for Simple Systems: Electrical and MechanicalSimplification Rules for Junction StructureDrawing Bond Graphs for Electrical SystemsDrawing Bond Graphs for Mechanical SystemsCausalityDrawing Bond Graphs for Hydraulic and Electronic Components and SystemsSome Basic Properties and Concepts for FluidsBond Graph Model of Hydraulic SystemsElectronic SystemsDeriving System Equations from Bond GraphsSystem VariablesDeriving System EquationsTackling Differential CausalityAlgebraic LoopsSolution of Model Equations and Their InterpretationZeroth Order SystemsFirst Order SystemsSecond Order SystemTransfer Functions and Frequency ResponsesNumerical Solution ...

  1. Polymer Soft-Landing Isolation of Acetylene on Polystyrene and Poly(vinylpyridine): A Novel Approach to Probing Hydrogen Bonding in Polymers.

    Science.gov (United States)

    Li, Yike; Samet, Cindy

    2015-09-17

    Hydrogen-bonded complexes of acetylene (Ac) with the polymers polystyrene (PS), poly(4-vinylpyridine) (P4VP), and poly(2-vinylpyridine) (P2VP) have been characterized for the first time at 16 K in a "polymer soft-landing isolation" experiment which is being pioneered in our research laboratory. In particular, changes in vibrational modes of Ac provide ample evidence for hydrogen-bonded complexes between Ac and the phenyl groups of PS or the pyridyl groups of P4VP and P2VP. With PS, the proton on the top Ac molecule of the classic T-shaped Ac dimer interacts with the π cloud of the benzene (Bz) ring to form a C-H---π interaction, while the π cloud of the lower Ac forms a second C-H---π interaction with a proton on the Bz ring. An analogous (ring)1-(Ac)2 double interaction occurs between an Ac dimer and the pyridine (Pyr) rings on both P2VP and P4VP, yielding a C-H---N and C-H---π interaction. With P4VP and P2VP a second bridged (ring)2-(Ac)2 product is formed, with the Ac dimer forming nearly collinear C-H---N hydrogen bonds to adjacent Pyr rings. On P2VP this bridged product is the only one after extensive annealing. These complexes in which Ac acts as both proton donor and acceptor have not previously been observed in conventional matrix isolation experiments. This study is the second from our laboratory employing this method, which represents a slight modification of the traditional matrix isolation technique.

  2. Australia's Bond Home Bias

    OpenAIRE

    Anil V. Mishra; Umaru B. Conteh

    2014-01-01

    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  3. Three approaches to investigating functional compromise to the default mode network after traumatic axonal injury.

    Science.gov (United States)

    Arenivas, Ana; Diaz-Arrastia, Ramon; Spence, Jeffrey; Cullum, C Munro; Krishnan, Kamini; Bosworth, Christopher; Culver, Carlee; Kennard, Beth; Marquez de la Plata, Carlos

    2014-09-01

    The default mode network (DMN) is a reliably elicited functional neural network with potential clinical implications. Its discriminant and prognostic utility following traumatic axonal injury (TAI) have not been previously investigated. The present study used three approaches to analyze DMN functional connectedness, including a whole-brain analysis [A1], network-specific analysis [A2], and between-node (edge) analysis [A3]. The purpose was to identify the utility of each method in distinguishing between healthy and brain-injured individuals, and determine whether observed differences have clinical significance. Resting-state fMRI was acquired from 25 patients with TAI and 17 healthy controls. Patients were scanned 6-11 months post-injury, and functional and neurocognitive outcomes were assessed the same day. Using all three approaches, TAI subjects revealed significantly weaker functional connectivity (FC) than controls, and binary logistic regressions demonstrated all three approaches have discriminant value. Clinical outcomes were not correlated with FC using any approach. Results suggest that compromise to the functional connectedness of the DMN after TAI can be identified using resting-state FC; however, the degree of functional compromise to this network, as measured in this study, may not have clinical implications in chronic TAI.

  4. A novel clinical approach for long-term retention and durability of resin restorations bonded to multiple developmental defects of enamel.

    Science.gov (United States)

    Harika, Rapala; Dutta, Brahmananda; Arun, Parsa; Teja, Raveen P

    2016-01-01

    Dental enamel is a unique, highly mineralized tissue of ectodermal origin. It is characterized by lack of metabolic activity once formed, implying that disturbances during development can manifest as permanent defects in the erupted tooth. Although the etiology of enamel defects may be attributed to local, systemic, genetic, or environmental factors, most are likely to be multifactorial in nature. The time frame of exposure and the mechanism underpinning the causative factors determine the presentation of these defects. These developmental defects of enamel (DDE) may range from slight abnormalities of the tooth's color to a complete absence of the enamel, some of which may be sensed by an individual as being disfiguring and call for treatment to improve the appearance of the dentition. Molar incisor hypomineralization (MIH) is a relatively common condition that varies in clinical severity, remains localized to permanent incisors and first permanent molars, and whose prevalence varies between 2.8 and 25% depending upon the study. Adhesion and retention of resin restorations is challenging in long-term rehabilitation in these cases. This paper presents a novel approach in the functional and esthetic rehabilitation of a 13-year-old female child diagnosed with multiple DDEs.

  5. A novel clinical approach for long-term retention and durability of resin restorations bonded to multiple developmental defects of enamel

    Science.gov (United States)

    Harika, Rapala; Dutta, Brahmananda; Arun, Parsa; Teja, Raveen P.

    2016-01-01

    Dental enamel is a unique, highly mineralized tissue of ectodermal origin. It is characterized by lack of metabolic activity once formed, implying that disturbances during development can manifest as permanent defects in the erupted tooth. Although the etiology of enamel defects may be attributed to local, systemic, genetic, or environmental factors, most are likely to be multifactorial in nature. The time frame of exposure and the mechanism underpinning the causative factors determine the presentation of these defects. These developmental defects of enamel (DDE) may range from slight abnormalities of the tooth's color to a complete absence of the enamel, some of which may be sensed by an individual as being disfiguring and call for treatment to improve the appearance of the dentition. Molar incisor hypomineralization (MIH) is a relatively common condition that varies in clinical severity, remains localized to permanent incisors and first permanent molars, and whose prevalence varies between 2.8 and 25% depending upon the study. Adhesion and retention of resin restorations is challenging in long-term rehabilitation in these cases. This paper presents a novel approach in the functional and esthetic rehabilitation of a 13-year-old female child diagnosed with multiple DDEs. PMID:28032054

  6. Human Bond Communication

    DEFF Research Database (Denmark)

    Prasad, Ramjee

    2016-01-01

    Modern dexterous communication technology is progressively enabling humans to communicate their information through them with speech (aural) and media (optical) as underpinning essence. Humans realize this kind of aural and optical information by their optical and auditory senses. However, due...... to certain constraints, the ability to incorporate the other three sensory features namely, olfactory, gustatory, and tactile are still far from reality. Human bond communication is a novel concept that incorporates olfactory, gustatory, and tactile that will allow more expressive and holistic sensory...... information exchange through communication techniques for more human sentiment centric communication. This concept endorses the need of inclusion of other three senses and proposes an innovative approach of holistic communication for future communication network....

  7. Organocatalysis by hydrogen-bonding: a new approach to controlled/living polymerization of α-amino acid N-carboxyanhydrides

    KAUST Repository

    Zhao, Wei

    2015-01-01

    A new method, based on hydrogen-bonding organocatalysis, was developed to achieve living ring-opening polymerization of N-carboxyanhydride of α-amino acids using aminoalcohols as initiators in the presence of N,N′-bis[3,5-bis(trifluoromethyl)phenyl]thiourea (TU-S). The thiourea provides, through hydrogen bonding, simultaneous activation of NCA monomers/reversible deactivation of polymer chain-ends/silencing of the tertiary amine and thus allows the polymerization to proceed in a highly controllable mode. For example, by using N,N-dimethyl ethanolamine (DMEA), as an initiator in the presence of TU-S, a series of well-defined linear polypeptides with differently designed Mns (3.01 × 104-18.10 × 104) and low PDI values (1.02-1.05) were successfully synthesized. This general strategy was also extended to the synthesis of well-defined di- and multi-armed polypeptides by using di-, tri-, or tetra-aminoalcohol initiators (methyldiethanolamine (MDEA), triethanolamine (TEA) or N,N,N′,N′-tetrakis(2-hydroxyethyl)ethylenediamine (THEED)) in the presence of TU-S. © The Royal Society of Chemistry 2015.

  8. Mining Functional Modules in Heterogeneous Biological Networks Using Multiplex PageRank Approach.

    Science.gov (United States)

    Li, Jun; Zhao, Patrick X

    2016-01-01

    Identification of functional modules/sub-networks in large-scale biological networks is one of the important research challenges in current bioinformatics and systems biology. Approaches have been developed to identify functional modules in single-class biological networks; however, methods for systematically and interactively mining multiple classes of heterogeneous biological networks are lacking. In this paper, we present a novel algorithm (called mPageRank) that utilizes the Multiplex PageRank approach to mine functional modules from two classes of biological networks. We demonstrate the capabilities of our approach by successfully mining functional biological modules through integrating expression-based gene-gene association networks and protein-protein interaction networks. We first compared the performance of our method with that of other methods using simulated data. We then applied our method to identify the cell division cycle related functional module and plant signaling defense-related functional module in the model plant Arabidopsis thaliana. Our results demonstrated that the mPageRank method is effective for mining sub-networks in both expression-based gene-gene association networks and protein-protein interaction networks, and has the potential to be adapted for the discovery of functional modules/sub-networks in other heterogeneous biological networks. The mPageRank executable program, source code, the datasets and results of the presented two case studies are publicly and freely available at http://plantgrn.noble.org/MPageRank/.

  9. An Approach to Function Annotation for Proteins of Unknown Function (PUFs in the Transcriptome of Indian Mulberry.

    Directory of Open Access Journals (Sweden)

    K H Dhanyalakshmi

    Full Text Available The modern sequencing technologies are generating large volumes of information at the transcriptome and genome level. Translation of this information into a biological meaning is far behind the race due to which a significant portion of proteins discovered remain as proteins of unknown function (PUFs. Attempts to uncover the functional significance of PUFs are limited due to lack of easy and high throughput functional annotation tools. Here, we report an approach to assign putative functions to PUFs, identified in the transcriptome of mulberry, a perennial tree commonly cultivated as host of silkworm. We utilized the mulberry PUFs generated from leaf tissues exposed to drought stress at whole plant level. A sequence and structure based computational analysis predicted the probable function of the PUFs. For rapid and easy annotation of PUFs, we developed an automated pipeline by integrating diverse bioinformatics tools, designated as PUFs Annotation Server (PUFAS, which also provides a web service API (Application Programming Interface for a large-scale analysis up to a genome. The expression analysis of three selected PUFs annotated by the pipeline revealed abiotic stress responsiveness of the genes, and hence their potential role in stress acclimation pathways. The automated pipeline developed here could be extended to assign functions to PUFs from any organism in general. PUFAS web server is available at http://caps.ncbs.res.in/pufas/ and the web service is accessible at http://capservices.ncbs.res.in/help/pufas.

  10. Oxo-functionalization and reduction of the uranyl ion through lanthanide-element bond homolysis: synthetic, structural, and bonding analysis of a series of singly reduced uranyl-rare earth 5f1-4f(n) complexes.

    Science.gov (United States)

    Arnold, Polly L; Hollis, Emmalina; Nichol, Gary S; Love, Jason B; Griveau, Jean-Christophe; Caciuffo, Roberto; Magnani, Nicola; Maron, Laurent; Castro, Ludovic; Yahia, Ahmed; Odoh, Samuel O; Schreckenbach, Georg

    2013-03-13

    The heterobimetallic complexes [{UO2Ln(py)2(L)}2], combining a singly reduced uranyl cation and a rare-earth trication in a binucleating polypyrrole Schiff-base macrocycle (Pacman) and bridged through a uranyl oxo-group, have been prepared for Ln = Sc, Y, Ce, Sm, Eu, Gd, Dy, Er, Yb, and Lu. These compounds are formed by the single-electron reduction of the Pacman uranyl complex [UO2(py)(H2L)] by the rare-earth complexes Ln(III)(A)3 (A = N(SiMe3)2, OC6H3Bu(t)2-2,6) via homolysis of a Ln-A bond. The complexes are dimeric through mutual uranyl exo-oxo coordination but can be cleaved to form the trimetallic, monouranyl "ate" complexes [(py)3LiOUO(μ-X)Ln(py)(L)] by the addition of lithium halides. X-ray crystallographic structural characterization of many examples reveals very similar features for monomeric and dimeric series, the dimers containing an asymmetric U2O2 diamond core with shorter uranyl U═O distances than in the monomeric complexes. The synthesis by Ln(III)-A homolysis allows [5f(1)-4f(n)]2 and Li[5f(1)-4f(n)] complexes with oxo-bridged metal cations to be made for all possible 4f(n) configurations. Variable-temperature SQUID magnetometry and IR, NIR, and EPR spectroscopies on the complexes are utilized to provide a basis for the better understanding of the electronic structure of f-block complexes and their f-electron exchange interactions. Furthermore, the structures, calculated by restricted-core or all-electron methods, are compared along with the proposed mechanism of formation of the complexes. A strong antiferromagnetic coupling between the metal centers, mediated by the oxo groups, exists in the U(V)Sm(III) monomer, whereas the dimeric U(V)Dy(III) complex was found to show magnetic bistability at 3 K, a property required for the development of single-molecule magnets.

  11. Hydrogen Bonds and Life in the Universe.

    Science.gov (United States)

    Vladilo, Giovanni; Hassanali, Ali

    2018-01-03

    The scientific community is allocating more and more resources to space missions and astronomical observations dedicated to the search for life beyond Earth. This experimental endeavor needs to be backed by a theoretical framework aimed at defining universal criteria for the existence of life. With this aim in mind, we have explored which chemical and physical properties should be expected for life possibly different from the terrestrial one, but similarly sustained by genetic and catalytic molecules. We show that functional molecules performing genetic and catalytic tasks must feature a hierarchy of chemical interactions operating in distinct energy bands. Of all known chemical bonds and forces, only hydrogen bonds are able to mediate the directional interactions of lower energy that are needed for the operation of genetic and catalytic tasks. For this reason and because of the unique quantum properties of hydrogen bonding, the functional molecules involved in life processes are predicted to have extensive hydrogen-bonding capabilities. A molecular medium generating a hydrogen-bond network is probably essential to support the activity of the functional molecules. These hydrogen-bond requirements constrain the viability of hypothetical biochemistries alternative to the terrestrial one, provide thermal limits to life molecular processes, and offer a conceptual framework to define a transition from a "covalent-bond stage" to a "hydrogen-bond stage" in prebiotic chemistry.

  12. Hydrogen Bonds and Life in the Universe

    Science.gov (United States)

    2018-01-01

    The scientific community is allocating more and more resources to space missions and astronomical observations dedicated to the search for life beyond Earth. This experimental endeavor needs to be backed by a theoretical framework aimed at defining universal criteria for the existence of life. With this aim in mind, we have explored which chemical and physical properties should be expected for life possibly different from the terrestrial one, but similarly sustained by genetic and catalytic molecules. We show that functional molecules performing genetic and catalytic tasks must feature a hierarchy of chemical interactions operating in distinct energy bands. Of all known chemical bonds and forces, only hydrogen bonds are able to mediate the directional interactions of lower energy that are needed for the operation of genetic and catalytic tasks. For this reason and because of the unique quantum properties of hydrogen bonding, the functional molecules involved in life processes are predicted to have extensive hydrogen-bonding capabilities. A molecular medium generating a hydrogen-bond network is probably essential to support the activity of the functional molecules. These hydrogen-bond requirements constrain the viability of hypothetical biochemistries alternative to the terrestrial one, provide thermal limits to life molecular processes, and offer a conceptual framework to define a transition from a “covalent-bond stage” to a “hydrogen-bond stage” in prebiotic chemistry. PMID:29301382

  13. New Medical Approach to Functional Dyspepsia, from Core Symposium 3, Japan Gastroenterological Association 2015-2017.

    Science.gov (United States)

    Suzuki, Hidekazu

    2018-01-01

    In the annual meeting of the Japan Gastroenterological Association (JGA), the scientific organizing committee selected the serial topics for the core symposium. One of the core symposia held during 2015-2017 was entitled "New medical approach to functional dyspepsia (FD)." In 2015, the subtitle of this symposium was "Helicobacter pylori gastritis and FD." In 2016, the subtitle of this symposium was "overlap with other functional GI disorders." In 2017, the subtitle was "therapeutic approach to FD." During these 3 years, a total of 24 presentations were included in Core Symposium 3 and deep and intensive discussions were carried out. © 2018 S. Karger AG, Basel.

  14. Bond-Slip Relationship for CFRP Sheets Externally Bonded to Concrete under Cyclic Loading.

    Science.gov (United States)

    Li, Ke; Cao, Shuangyin; Yang, Yue; Zhu, Juntao

    2018-02-26

    The objective of this paper was to explore the bond-slip relationship between carbon fiber-reinforced polymer (CFRP) sheets and concrete under cyclic loading through experimental and analytical approaches. Modified beam tests were performed in order to gain insight into the bond-slip relationship under static and cyclic loading. The test variables are the CFRP-to-concrete width ratio, and the bond length of the CFRP sheets. An analysis of the test results in this paper and existing test results indicated that the slope of the ascending segment of the bond-slip curve decreased with an increase in the number of load cycles, but the slip corresponding to the maximum shear stress was almost invariable as the number of load cycles increased. In addition, the rate of reduction in the slope of the ascending range of the bond-slip curve during cyclic loading decreased as the concrete strength increased, and increased as the load level or CFRP-to-concrete width ratio enhanced. However, these were not affected by variations in bond length if the residual bond length was longer than the effective bond length. A bilinear bond-slip model for CFRP sheets that are externally bonded to concrete under cyclic loading, which considered the effects of the cyclic load level, concrete strength, and CFRP-to-concrete ratio, was developed based on the existing static bond-slip model. The accuracy of this proposed model was verified by a comparison between this proposed model and test results.

  15. Selective Hydrogen Atom Abstraction via Induced Bond Polarization: The Direct -Arylation of Alcohols via Photoredox, HAT and Nickel Catalysis.

    Science.gov (United States)

    Twilton, Jack; Christensen, Melodie; DiRocco, Daniel A; Ruck, Rebecca T; Davies, Ian W; MacMillan, David William

    2018-02-28

    The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation protocol for the selective functionalization of alcohol -hydroxy C-H bonds. This approach employs zinc-mediated alcohol deprotonation to activate -hydroxy C-H bonds while simultaneously suppressing C-O bond formation by inhibiting formation of nickel alkoxide species. The use of Zn based Lewis acids also deactivates other hydridic bonds such as -amino and -oxy C-H bonds. This technology facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3-step synthesis of the Prozac exemplifies the utility of this new method. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. The structure and dynamics of the Fe-CO bond in myoglobin

    International Nuclear Information System (INIS)

    Rovira, Carme

    2003-01-01

    This paper is a review of our recent work on the structure and dynamics of the Fe-CO bond in carbonmonoxy myoglobin (MbCO), performed using density functional theory, Car-Parrinello molecular dynamics and hybrid quantum mechanics/molecular mechanics approaches. The results of these investigations have served to shed light onto one of the long standing questions in myoglobin research: whether the protein discriminates the CO ligand with respect to O 2 by distorting the FeCO bond. The calculations show that both in the gas phase and in the protein the Fe-CO bond is essentially linear and therefore exclude the hypothesis that the CO in MbCO is sterically hindered. In contrast, hydrogen bonding between the O 2 ligand and the His64 residue easily explains the protein discrimination for CO

  17. Alternative approach to automated management of load flow in engineering networks considering functional reliability

    Directory of Open Access Journals (Sweden)

    Ирина Александровна Гавриленко

    2016-02-01

    Full Text Available The approach to automated management of load flow in engineering networks considering functional reliability was proposed in the article. The improvement of the concept of operational and strategic management of load flow in engineering networks was considered. The verbal statement of the problem for thesis research is defined, namely, the problem of development of information technology for exact calculation of the functional reliability of the network, or the risk of short delivery of purpose-oriented product for consumers

  18. Modeling the vapor-liquid equilibria of polymer-solvent mixtures: Systems with complex hydrogen bonding behavior

    DEFF Research Database (Denmark)

    Tsivintzelis, Ioannis; Kontogeorgis, Georgios

    2009-01-01

    The vapor–liquid equilibria of binary polymer–solvent systems was modeled using the Non-Random Hydrogen Bonding (NRHB) model. Mixtures of poly(ethylene glycol), poly(propylene glycol), poly(vinyl alcohol) and poly(vinyl acetate) with various solvents were investigated, while emphasis was put...... on hydrogen bonding systems, in which functional groups of the polymer chain can self-associate or cross-associate with the solvent molecules. Effort has been made to explicitly account for all hydrogen bonding interactions. The results reveal that the NRHB model offers a flexible approach to account...

  19. Scientific and methodic approaches to reveal stability essence at the industrial enterprises and its functional components

    Directory of Open Access Journals (Sweden)

    Lyulyov Oleksii Valentynovych

    2016-12-01

    Full Text Available The article deals with theoretical analysis of the scientific approaches concerning definition of the concept “stability”, which exist in the scientific literature. There are five different approaches to interpret the concept “enterprise stability”, as an open economic system. On this base, the author’s definition of the enterprise stability is formed. Due to the carried out analysis of the main tendencies in changes of the industry development factors for 2006-2015 and future expectations, the main functional constituents of the enterprise stability. The author suggests to use an approach of self-organizational artificial neural networks to evaluate stability degree at the industrial enterprises.

  20. Formation of a metal-to-nitrogen bond of normal length by a neutral sufonamide group within a tridentate ligand. A new approach to radiopharmaceutical bioconjugation.

    Science.gov (United States)

    Perera, Theshini; Abhayawardhana, Pramuditha; Marzilli, Patricia A; Fronczek, Frank R; Marzilli, Luigi G

    2013-03-04

    We demonstrate that a tertiary sulfonamide group, N(SO2R)R'2, can rehybridize to form a M-N bond of normal length even when the group is in a linear tridentate ligand, such as in the new tridentate N(SO2R)dpa ligands derived from di-(2-picolyl)amine (N(H)dpa). N(SO2R)dpa ligands were used to prepare fac-[Re(CO)3(N(SO2R)dpa)](PF6 or BF4) complexes. Structural characterization of the new complexes established that the tertiary sulfonamide nitrogen atom binds to Re with concomitant sp(2)-to-sp(3) rehybridization, facilitating facial coordination. The new fac-[Re(CO)3(N(SO2R)dpa)]X structures provide the only examples for any metal with the sulfonamide as part of a noncyclic linear tridentate ligand and with a normal metal-to-nitrogen(tertiary sulfonamide) bond length. Rare previous examples of such normal M-N bonds have been found only in more constrained situations, such as with tripodal tetradentate ligands. Our long-term objectives for the new tridentate N(SO2R)dpa ligands are to develop the fundamental chemistry relevant to the eventual use of the fac-[M(I)(CO)3](+) core (M = (99m)Tc, (186/188)Re) in imaging and therapy. The sulfonamide group uniquely contributes to two of our goals: expanding ways to conjugate the fac-[M(I)(CO)3](+) core to biological molecules and also developing new symmetrical tridentate ligands that can coordinate facially to this core. Tests of our conjugation method, conducted by linking the fac-[Re(I)(CO)3](+) core to a new tetraarylporphyrin (T(N(SO2C6H4)dpa)P) as well as to a dansyl (5-(dimethylamino)naphthalene-1-sulfonyl) group, demonstrate that large molecular fragments can be tethered via a coordinated tertiary sulfonamide linkage to this core.

  1. An improved α-cut approach to transforming fuzzy membership function into basic belief assignment

    Directory of Open Access Journals (Sweden)

    Yang Yi

    2016-08-01

    Full Text Available In practical applications, pieces of evidence originated from different sources might be modeled by different uncertainty theories. To implement the evidence combination under the Dempster–Shafer evidence theory (DST framework, transformations from the other type of uncertainty representation into the basic belief assignment are needed. α-Cut is an important approach to transforming a fuzzy membership function into a basic belief assignment, which provides a bridge between the fuzzy set theory and the DST. Some drawbacks of the traditional α-cut approach caused by its normalization step are pointed out in this paper. An improved α-cut approach is proposed, which can counteract the drawbacks of the traditional α-cut approach and has good properties. Illustrative examples, experiments and related analyses are provided to show the rationality of the improved α-cut approach.

  2. Integrative approaches to the prediction of protein functions based on the feature selection

    Directory of Open Access Journals (Sweden)

    Lee Hyunju

    2009-12-01

    Full Text Available Abstract Background Protein function prediction has been one of the most important issues in functional genomics. With the current availability of various genomic data sets, many researchers have attempted to develop integration models that combine all available genomic data for protein function prediction. These efforts have resulted in the improvement of prediction quality and the extension of prediction coverage. However, it has also been observed that integrating more data sources does not always increase the prediction quality. Therefore, selecting data sources that highly contribute to the protein function prediction has become an important issue. Results We present systematic feature selection methods that assess the contribution of genome-wide data sets to predict protein functions and then investigate the relationship between genomic data sources and protein functions. In this study, we use ten different genomic data sources in Mus musculus, including: protein-domains, protein-protein interactions, gene expressions, phenotype ontology, phylogenetic profiles and disease data sources to predict protein functions that are labelled with Gene Ontology (GO terms. We then apply two approaches to feature selection: exhaustive search feature selection using a kernel based logistic regression (KLR, and a kernel based L1-norm regularized logistic regression (KL1LR. In the first approach, we exhaustively measure the contribution of each data set for each function based on its prediction quality. In the second approach, we use the estimated coefficients of features as measures of contribution of data sources. Our results show that the proposed methods improve the prediction quality compared to the full integration of all data sources and other filter-based feature selection methods. We also show that contributing data sources can differ depending on the protein function. Furthermore, we observe that highly contributing data sets can be similar among

  3. Fragment approach to constrained density functional theory calculations using Daubechies wavelets

    International Nuclear Information System (INIS)

    Ratcliff, Laura E.; Genovese, Luigi; Mohr, Stephan; Deutsch, Thierry

    2015-01-01

    In a recent paper, we presented a linear scaling Kohn-Sham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix of the system can be projected. In this paper, we demonstrate the flexibility of this minimal basis formalism in providing a basis set that can be reused as-is, i.e., without reoptimization, for charge-constrained DFT calculations within a fragment approach. Support functions, represented in the underlying wavelet grid, of the template fragments are roto-translated with high numerical precision to the required positions and used as projectors for the charge weight function. We demonstrate the interest of this approach to express highly precise and efficient calculations for preparing diabatic states and for the computational setup of systems in complex environments

  4. Functional approach to a Class II patient with upper first molar impaction

    Directory of Open Access Journals (Sweden)

    Giacomo D′Orlandi

    2014-01-01

    Full Text Available The lack of the left first molar maxillary and the left second molar maxillary, caused respectively by impaction and agenesis is a very rare case, which determines an important occlusal imbalance and asymmetrical mandible movement. A gnatologic and functional orthodontic approach were planned to improve the retrognathic mandible and the muscular activity using kinesiograph and electromyography.

  5. FeedOmics, an approach to evaluate the functional properties of protein containing feed ingredients

    NARCIS (Netherlands)

    Kar, Soumya K.

    2017-01-01

    This thesis presents FeedOmics approach as a toolkit, to evaluate (novel) protein containing feed ingredients of different origin considering both their nutritional and functional value in terms of their capacity to support or modify nutrient supply, the animal’s physiology, tissue development

  6. A functional genomics approach using metabolomics and in silico pathway analysis

    DEFF Research Database (Denmark)

    Förster, Jochen; Gombert, Andreas Karoly; Nielsen, Jens

    2002-01-01

    analysis techniques and changes in the genotype will in many cases lead to different metabolite profiles. Here, a theoretical framework that may be applied to identify the function of orphan genes is presented. The approach is based on a combination of metabolome analysis combined with in silico pathway...

  7. The Dietary Approaches to Stop Hypertension Diet, Cognitive Function, and Cognitive Decline in American Older Women

    NARCIS (Netherlands)

    Berendsen, A.M.; Kang, Jae H.; Rest, van de O.; Feskens, E.J.M.; Groot, de C.P.G.M.; Grodstein, F.

    2017-01-01

    ObjectivesTo examine the association between long-term adherence to the Dietary Approaches to Stop Hypertension (DASH) diet with cognitive function and decline in older American women.DesignProspective cohort study.SettingThe Nurses' Health Study, a cohort of registered nurses residing in 11 US

  8. Novel Vaccine Approach Achieves “Functional Cure” of AIDS Virus in Monkeys | Poster

    Science.gov (United States)

    By Frank Blanchard, Staff Writer, and Jeff Lifson, Guest Writer Scientists at the Oregon Health & Science University and the AIDS and Cancer Virus Program of the Frederick National Laboratory for Cancer Research have used a novel vaccine approach to achieve a “functional cure” and apparent eradication of infection with a monkey version of the AIDS virus.

  9. Towards an open functional approach to welfare state change: Pressures, ideas, and blame avoidance

    NARCIS (Netherlands)

    Vis, B.; van Kersbergen, C.J.

    2013-01-01

    Why are some governments able to push through radical welfare state reforms while others, operating in similar circumstances, are not? Why are some ideas more acceptable than others? We present an open functional approach to reform to answer these questions and illustrate it empirically by

  10. An approach for functional safety improvement of an existing automotive system

    NARCIS (Netherlands)

    Khabbaz Saberi, A.; Luo, Y.; Pawel Cichosz, F.; Brand, M. van den; Jansen, S.T.H.

    2015-01-01

    Safety of automotive systems is becoming more involved, specially for the case of autonomous vehicles. The ISO 26262 standard offers a systematic approach for designing a safe road vehicle (or subsystems of a car) from design phase through its production. However, providing functional safety

  11. Identification of differential item functioning in multiple-group settings: a multivariate outlier detection approach

    NARCIS (Netherlands)

    Magis, D.; de Boeck, P.

    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

  12. CONFAC Decomposition Approach to Blind Identification of Underdetermined Mixtures Based on Generating Function Derivatives

    NARCIS (Netherlands)

    de Almeida, Andre L. F.; Luciani, Xavier; Stegeman, Alwin; Comon, Pierre

    2012-01-01

    This work proposes a new tensor-based approach to solve the problem of blind identification of underdetermined mixtures of complex-valued sources exploiting the cumulant generating function (CGF) of the observations. We show that a collection of second-order derivatives of the CGF of the

  13. A Unified Theory for the Blue- and Red-Shifting Phenomena in Hydrogen and Halogen Bonds.

    Science.gov (United States)

    Wang, Changwei; Danovich, David; Shaik, Sason; Mo, Yirong

    2017-04-11

    Typical hydrogen and halogen bonds exhibit red-shifts of their vibrational frequencies upon the formation of hydrogen and halogen bonding complexes (denoted as D···Y-A, Y = H and X). The finding of blue-shifts in certain complexes is of significant interest, which has led to numerous studies of the origins of the phenomenon. Because charge transfer mixing (i.e., hyperconjugation in bonding systems) has been regarded as one of the key forces, it would be illuminating to compare the structures and vibrational frequencies in bonding complexes with the charge transfer effect "turned on" and "turned off". Turning off the charge transfer mixing can be achieved by employing the block-localized wave function (BLW) method, which is an ab initio valence bond (VB) method. Further, with the BLW method, the overall stability gained in the formation of a complex can be analyzed in terms of a few physically meaningful terms. Thus, the BLW method provides a unified and physically lucid way to explore the nature of red- and blue-shifting phenomena in both hydrogen and halogen bonding complexes. In this study, a direct correlation between the total stability and the variation of the Y-A bond length is established based on our BLW computations, and the consistent roles of all energy components are clarified. The n(D) → σ*(Y-A) electron transfer stretches the Y-A bond, while the polarization due to the approach of interacting moieties reduces the HOMO-LUMO gap and results in a stronger orbital mixing within the YA monomer. As a consequence, both the charge transfer and polarization stabilize bonding systems with the Y-A bond stretched and red-shift the vibrational frequency of the Y-A bond. Notably, the energy of the frozen wave function is the only energy component which prefers the shrinking of the Y-A bond and thus is responsible for the associated blue-shifting. The total variations of the Y-A bond length and the corresponding stretching vibrational frequency are thus

  14. Modeling single molecule junction mechanics as a probe of interface bonding

    Science.gov (United States)

    Hybertsen, Mark S.

    2017-03-01

    Using the atomic force microscope based break junction approach, applicable to metal point contacts and single molecule junctions, measurements can be repeated thousands of times resulting in rich data sets characterizing the properties of an ensemble of nanoscale junction structures. This paper focuses on the relationship between the measured force extension characteristics including bond rupture and the properties of the interface bonds in the junction. A set of exemplary model junction structures has been analyzed using density functional theory based calculations to simulate the adiabatic potential surface that governs the junction elongation. The junction structures include representative molecules that bond to the electrodes through amine, methylsulfide, and pyridine links. The force extension characteristics are shown to be most effectively analyzed in a scaled form with maximum sustainable force and the distance between the force zero and force maximum as scale factors. Widely used, two parameter models for chemical bond potential energy versus bond length are found to be nearly identical in scaled form. Furthermore, they fit well to the present calculations of N-Au and S-Au donor-acceptor bonds, provided no other degrees of freedom are allowed to relax. Examination of the reduced problem of a single interface, but including relaxation of atoms proximal to the interface bond, shows that a single-bond potential form renormalized by an effective harmonic potential in series fits well to the calculated results. This allows relatively accurate extraction of the interface bond energy. Analysis of full junction models shows cooperative effects that go beyond the mechanical series inclusion of the second bond in the junction, the spectator bond that does not rupture. Calculations for a series of diaminoalkanes as a function of molecule length indicate that the most important cooperative effect is due to the interactions between the dipoles induced by the donor

  15. Density functional response approach for the linear and nonlinear electric properties of molecules

    Science.gov (United States)

    Sophy, K. B.; Pal, Sourav

    2003-06-01

    This is a preliminary study toward implementation of analytic density functional response approach for molecules to obtain linear and nonlinear electric properties. The Kohn-Sham framework has been used with Gaussian basis sets. We propose a fully variational approach to obtain the response of electronic density in terms of the atomic orbital basis (contracted Gaussians). As a first step, this derivative of the Kohn-Sham operator is obtained by a finite field method using five different values of electric field. Using this, we obtain the energy derivatives up to third order using fully analytic expressions. We calculate the dipole moment, polarizability, and hyperpolarizability of the hydrogen fluoride (HF) molecule as a test case using different exchange-correlation functionals and basis sets within the present methodology. We also explore the feasibility of this response approach by studying the properties of the HF molecule for different H-F distances.

  16. Electron transfer in pnicogen bonds.

    Science.gov (United States)

    Guan, Liangyu; Mo, Yirong

    2014-10-02

    As a new type of noncovalent interactions, pnicogen bond between a VA group element (N, P, and As) and an electron donor (Lewis base) has grabbed attention in recent several years. Here we employ the block-localized wave function (BLW) based energy decomposition scheme to probe the bonding nature in a series of substituted phosphines X(n)PH(3-n) complexed with ammonia. As the BLW method can derive the optimal monomer orbitals in a complex with the electron transfer among monomers quenched, we can effectively examine the HOMO-LUMO interaction in these pnicogen bonding systems. Among various energy components, electron transfer energy together with the polarization energy dominates the pnicogen bonding energy. Although usually it is assumed that the electron transfer from ammonia to substituted phosphines occurs in the form of n → σ*(XP) hyperconjugative interaction, we identify a kind of new pathway when X = NO2 and CN, i.e., n → dπ*, which results from the interaction between the π orbital of cyano or nitro substituent and d orbitals on P. But still this picture of electron transfer using a single pair of orbitals is greatly simplified, as the electron density difference (EDD) maps corresponding to the overall electron transfer processes show the accumulation of electron density on the P side opposite to the X-P bond, with insignificant or even negligible gain of electron density on the substituent group side. Thus, the EDD maps tend to support the concept of σ-hole in pnicogen bonds.

  17. A Functional Approach to Compiling a Specialized English–Slovene Dictionary of Green Energy Terms

    Directory of Open Access Journals (Sweden)

    Laura Mrhar

    2013-05-01

    Full Text Available The functional approach to lexicography argues that dictionaries must provide their users with concrete types of information, presented in a manner that suits their needs. To achieve this, the process of compiling specialized dictionaries must be improved. This paper examines the revision of a specialized English–Slovene Dictionary of Green Energy Terms, with particular emphasis on the functional approach to building specialized dictionaries. As the potential users of the unrevised dictionary differ from those of the revised version, this paper aims to show how the profile of the intended user affects the structure of the actual dictionary entry, as well as the dictionary’s main functions. The main objective of the paper is therefore to put forward a sound theoretical foundation for the improved construction of LSP dictionaries, so that they will truly serve as a helpful tool in solving those problems that normally occur in LSP communication.

  18. Measuring the immune system: a comprehensive approach for the analysis of immune functions in humans.

    Science.gov (United States)

    Claus, Maren; Dychus, Nicole; Ebel, Melanie; Damaschke, Jürgen; Maydych, Viktoriya; Wolf, Oliver T; Kleinsorge, Thomas; Watzl, Carsten

    2016-10-01

    The immune system is essential to provide protection from infections and cancer. Disturbances in immune function can therefore directly affect the health of the affected individual. Many extrinsic and intrinsic factors such as exposure to chemicals, stress, nutrition and age have been reported to influence the immune system. These influences can affect various components of the immune system, and we are just beginning to understand the causalities of these changes. To investigate such disturbances, it is therefore essential to analyze the different components of the immune system in a comprehensive fashion. Here, we demonstrate such an approach which provides information about total number of leukocytes, detailed quantitative and qualitative changes in the composition of lymphocyte subsets, cytokine levels in serum and functional properties of T cells, NK cells and monocytes. Using samples from a cohort of 24 healthy volunteers, we demonstrate the feasibility of our approach to detect changes in immune functions.

  19. Scale-dependence of processes structuring dung beetle metacommunities using functional diversity and community deconstruction approaches.

    Directory of Open Access Journals (Sweden)

    Pedro Giovâni da Silva

    Full Text Available Community structure is driven by mechanisms linked to environmental, spatial and temporal processes, which have been successfully addressed using metacommunity framework. The relative importance of processes shaping community structure can be identified using several different approaches. Two approaches that are increasingly being used are functional diversity and community deconstruction. Functional diversity is measured using various indices that incorporate distinct community attributes. Community deconstruction is a way to disentangle species responses to ecological processes by grouping species with similar traits. We used these two approaches to determine whether they are improvements over traditional measures (e.g., species composition, abundance, biomass for identification of the main processes driving dung beetle (Scarabaeinae community structure in a fragmented mainland-island landscape in southern Brazilian Atlantic Forest. We sampled five sites in each of four large forest areas, two on the mainland and two on the island. Sampling was performed in 2012 and 2013. We collected abundance and biomass data from 100 sampling points distributed over 20 sampling sites. We studied environmental, spatial and temporal effects on dung beetle community across three spatial scales, i.e., between sites, between areas and mainland-island. The γ-diversity based on species abundance was mainly attributed to β-diversity as a consequence of the increase in mean α- and β-diversity between areas. Variation partitioning on abundance, biomass and functional diversity showed scale-dependence of processes structuring dung beetle metacommunities. We identified two major groups of responses among 17 functional groups. In general, environmental filters were important at both local and regional scales. Spatial factors were important at the intermediate scale. Our study supports the notion of scale-dependence of environmental, spatial and temporal processes in

  20. Scale-dependence of processes structuring dung beetle metacommunities using functional diversity and community deconstruction approaches.

    Science.gov (United States)

    Silva, Pedro Giovâni da; Hernández, Malva Isabel Medina

    2015-01-01

    Community structure is driven by mechanisms linked to environmental, spatial and temporal processes, which have been successfully addressed using metacommunity framework. The relative importance of processes shaping community structure can be identified using several different approaches. Two approaches that are increasingly being used are functional diversity and community deconstruction. Functional diversity is measured using various indices that incorporate distinct community attributes. Community deconstruction is a way to disentangle species responses to ecological processes by grouping species with similar traits. We used these two approaches to determine whether they are improvements over traditional measures (e.g., species composition, abundance, biomass) for identification of the main processes driving dung beetle (Scarabaeinae) community structure in a fragmented mainland-island landscape in southern Brazilian Atlantic Forest. We sampled five sites in each of four large forest areas, two on the mainland and two on the island. Sampling was performed in 2012 and 2013. We collected abundance and biomass data from 100 sampling points distributed over 20 sampling sites. We studied environmental, spatial and temporal effects on dung beetle community across three spatial scales, i.e., between sites, between areas and mainland-island. The γ-diversity based on species abundance was mainly attributed to β-diversity as a consequence of the increase in mean α- and β-diversity between areas. Variation partitioning on abundance, biomass and functional diversity showed scale-dependence of processes structuring dung beetle metacommunities. We identified two major groups of responses among 17 functional groups. In general, environmental filters were important at both local and regional scales. Spatial factors were important at the intermediate scale. Our study supports the notion of scale-dependence of environmental, spatial and temporal processes in the distribution

  1. Molecular Orbital and Density Functional Study of the Formation, Charge Transfer, Bonding and the Conformational Isomerism of the Boron Trifluoride (BF3 and Ammonia (NH3 Donor-Acceptor Complex

    Directory of Open Access Journals (Sweden)

    Dulal C. Ghosh

    2004-09-01

    Full Text Available The formation of the F3B–NH3 supermolecule by chemical interaction of its fragment parts, BF3 and NH3, and the dynamics of internal rotation about the ‘B–N’ bond have been studied in terms of parameters provided by the molecular orbital and density functional theories. It is found that the pairs of frontier orbitals of the interacting fragments have matching symmetry and are involved in the charge transfer interaction. The donation process stems from the HOMO of the donor into the LUMO of the acceptor and simultaneously, back donation stems from the HOMO of acceptor into the LUMO of the donor. The density functional computation of chemical activation in the donor and acceptor fragments, associated with the physical process of structural reorganization just prior to the event of chemical reaction, indicates that BF3 becomes more acidic and NH3 becomes more basic, compared to their separate equilibrium states. Theoretically it is observed that the chemical reaction event of the formation of the supermolecule from its fragment parts is in accordance with the chemical potential equalization principle of the density functional theory and the electronegativity equalization principle of Sanderson. The energetics of the chemical reaction, the magnitude of the net charge transfer and the energy of the newly formed bond are quite consistent, both internally and with the principle of maximum hardness, PMH. The dynamics of the internal rotation of one part with respect to the other part of the supermolecule about the ‘B–N’ bond mimics the pattern of the conformational isomerism of the isostructural ethane molecule. It is also observed that the dynamics and evolution of molecular conformations as a function of dihedral angles is also in accordance with the principle of maximum hardness, PMH. Quite consistent with spectroscopic predictions, the height of the molecule

  2. Supramolecular network through Nsbnd H…O, Osbnd H…O and Csbnd H…O hydrogen bonding interaction and density functional theory studies of 4-methylanilinium-3-carboxy-4-hydroxybenzenesulphonate crystal

    Science.gov (United States)

    Rajkumar, M.; Muthuraja, P.; Dhandapani, M.; Chandramohan, A.

    2018-02-01

    By utilizing the hydrogen bonding strategy, 4-methylanilinium-3-hydroxy-4-corboxy-benzenesulphonate (4MABS), an organic proton transfer molecular salt was synthesized and single crystals of it were successfully grown by slow solvent evaporation solution growth technique at ambient temperature. The 1H and 13C NMR spectra were recorded to establish the molecular structure of the title salt. The single crystal XRD analysis reveals that the title salt crystallizes in monoclinic crystal system with centrosymmetric space group, P21/n. Further, the title salt involves extensive intermolecular Nsbnd H…O, Osbnd H…O and Csbnd H…O as well as intramolecular Osbnd H…O hydrogen bonding interactions to construct supramolecular architecture. All quantum chemical calculations were performed at the level of density functional theory (DFT) with B3LYP functional using 6-311G (d,p) basis atomic set. The photoluminescence spectrum was recorded to explore the emission property of the title crystal. The presence of the various vibrational modes and functional groups in the synthesized salt was confirmed by FT-IR studies. The thermal behaviour of title crystal was established employing TG/DTA analyses. The mechanical properties of the grown crystal were determined by Vicker's microhardness studies. Dielectric measurements were carried out on the grown crystal at a different temperature to evaluate electrical properties.

  3. A general method for the derivation of the functional forms of the effective energy terms in coarse-grained energy functions of polymers. II. Backbone-local potentials of coarse-grained O1→4-bonded polyglucose chains.

    Science.gov (United States)

    Lubecka, Emilia A; Liwo, Adam

    2017-09-21

    Based on the theory of the construction of coarse-grained force fields for polymer chains described in our recent work [A. K. Sieradzan et al., J. Chem. Phys. 146, 124106 (2017)], in this work effective coarse-grained potentials, to be used in the SUGRES-1P model of polysaccharides that is being developed in our laboratory, have been determined for the O⋯O⋯O virtual-bond angles (θ) and for the dihedral angles for rotation about the O⋯O virtual bonds (γ) of 1 → 4-linked glucosyl polysaccharides, for all possible combinations of [α,β]-[d,l]-glucose. The potentials of mean force corresponding to the virtual-bond angles and the virtual-bond dihedral angles were calculated from the free-energy surfaces of [α,β]-[d,l]-glucose pairs, determined by umbrella-sampling molecular-dynamics simulations with the AMBER12 force field, or combinations of the surfaces of two pairs sharing the overlapping residue, respectively, by integrating the respective Boltzmann factor over the dihedral angles λ for the rotation of the sugar units about the O⋯O virtual bonds. Analytical expressions were subsequently fitted to the potentials of mean force. The virtual-bond-torsional potentials depend on both virtual-bond-dihedral angles and virtual-bond angles. The virtual-bond-angle potentials contain a single minimum at about θ=140 ° for all pairs except β-d-[α,β]-l-glucose, where the global minimum is shifted to θ=150 ° and a secondary minimum appears at θ=90 ° . The torsional potentials favor small negative γ angles for the α-d-glucose and extended negative angles γ for the β-d-glucose chains, as observed in the experimental structures of starch and cellulose, respectively. It was also demonstrated that the approximate expression derived based on Kubo's cluster-cumulant theory, whose coefficients depend on the identity of the disugar units comprising a trisugar unit that defines a torsional potential, fits simultaneously all torsional potentials very well

  4. A general method for the derivation of the functional forms of the effective energy terms in coarse-grained energy functions of polymers. II. Backbone-local potentials of coarse-grained O 1 →4 -bonded polyglucose chains

    Science.gov (United States)

    Lubecka, Emilia A.; Liwo, Adam

    2017-09-01

    Based on the theory of the construction of coarse-grained force fields for polymer chains described in our recent work [A. K. Sieradzan et al., J. Chem. Phys. 146, 124106 (2017)], in this work effective coarse-grained potentials, to be used in the SUGRES-1P model of polysaccharides that is being developed in our laboratory, have been determined for the O ⋯O ⋯O virtual-bond angles (θ ) and for the dihedral angles for rotation about the O ⋯O virtual bonds (γ ) of 1 → 4 -linked glucosyl polysaccharides, for all possible combinations of [α ,β ]-[d,l]-glucose. The potentials of mean force corresponding to the virtual-bond angles and the virtual-bond dihedral angles were calculated from the free-energy surfaces of [α ,β ]-[d,l]-glucose pairs, determined by umbrella-sampling molecular-dynamics simulations with the AMBER12 force field, or combinations of the surfaces of two pairs sharing the overlapping residue, respectively, by integrating the respective Boltzmann factor over the dihedral angles λ for the rotation of the sugar units about the O ⋯O virtual bonds. Analytical expressions were subsequently fitted to the potentials of mean force. The virtual-bond-torsional potentials depend on both virtual-bond-dihedral angles and virtual-bond angles. The virtual-bond-angle potentials contain a single minimum at about θ =14 0° for all pairs except β -d-[α ,β ] -l-glucose, where the global minimum is shifted to θ =150° and a secondary minimum appears at θ =90°. The torsional potentials favor small negative γ angles for the α -d-glucose and extended negative angles γ for the β -d-glucose chains, as observed in the experimental structures of starch and cellulose, respectively. It was also demonstrated that the approximate expression derived based on Kubo's cluster-cumulant theory, whose coefficients depend on the identity of the disugar units comprising a trisugar unit that defines a torsional potential, fits simultaneously all

  5. Representational Classroom Practices that Contribute to Students' Conceptual and Representational Understanding of Chemical Bonding

    Science.gov (United States)

    Hilton, Annette; Nichols, Kim

    2011-11-01

    Understanding bonding is fundamental to success in chemistry. A number of alternative conceptions related to chemical bonding have been reported in the literature. Research suggests that many alternative conceptions held by chemistry students result from previous teaching; if teachers are explicit in the use of representations and explain their content-specific forms and functions, this might be avoided. The development of an understanding of and ability to use multiple representations is crucial to students' understanding of chemical bonding. This paper draws on data from a larger study involving two Year 11 chemistry classes (n = 27, n = 22). It explores the contribution of explicit instruction about multiple representations to students' understanding and representation of chemical bonding. The instructional strategies were documented using audio-recordings and the teacher-researcher's reflection journal. Pre-test-post-test comparisons showed an improvement in conceptual understanding and representational competence. Analysis of the students' texts provided further evidence of the students' ability to use multiple representations to explain macroscopic phenomena on the molecular level. The findings suggest that explicit instruction about representational form and function contributes to the enhancement of representational competence and conceptual understanding of bonding in chemistry. However, the scaffolding strategies employed by the teacher play an important role in the learning process. This research has implications for professional development enhancing teachers' approaches to these aspects of instruction around chemical bonding.

  6. Efficient Variational Approach to Multimodal Registration of Anatomical and Functional Intra-Patient Tumorous Brain Data.

    Science.gov (United States)

    Legaz-Aparicio, Alvar-Ginés; Verdú-Monedero, Rafael; Larrey-Ruiz, Jorge; Morales-Sánchez, Juan; López-Mir, Fernando; Naranjo, Valery; Bernabéu, Ángela

    2017-09-01

    This paper addresses the functional localization of intra-patient images of the brain. Functional images of the brain (fMRI and PET) provide information about brain function and metabolism whereas anatomical images (MRI and CT) supply the localization of structures with high spatial resolution. The goal is to find the geometric correspondence between functional and anatomical images in order to complement and fuse the information provided by each imaging modality. The proposed approach is based on a variational formulation of the image registration problem in the frequency domain. It has been implemented as a C/C[Formula: see text] library which is invoked from a GUI. This interface is routinely used in the clinical setting by physicians for research purposes (Inscanner, Alicante, Spain), and may be used as well for diagnosis and surgical planning. The registration of anatomic and functional intra-patient images of the brain makes it possible to obtain a geometric correspondence which allows for the localization of the functional processes that occur in the brain. Through 18 clinical experiments, it has been demonstrated how the proposed approach outperforms popular state-of-the-art registration methods in terms of efficiency, information theory-based measures (such as mutual information) and actual registration error (distance in space of corresponding landmarks).

  7. A Multimodal Approach for Determining Brain Networks by Jointly Modeling Functional and Structural Connectivity

    Directory of Open Access Journals (Sweden)

    Wenqiong eXue

    2015-02-01

    Full Text Available Recent innovations in neuroimaging technology have provided opportunities for researchers to investigate connectivity in the human brain by examining the anatomical circuitry as well as functional relationships between brain regions. Existing statistical approaches for connectivity generally examine resting-state or task-related functional connectivity (FC between brain regions or separately examine structural linkages. As a means to determine brain networks, we present a unified Bayesian framework for analyzing FC utilizing the knowledge of associated structural connections, which extends an approach by Patel et al.(2006a that considers only functional data. We introduce an FC measure that rests upon assessments of functional coherence between regional brain activity identified from functional magnetic resonance imaging (fMRI data. Our structural connectivity (SC information is drawn from diffusion tensor imaging (DTI data, which is used to quantify probabilities of SC between brain regions. We formulate a prior distribution for FC that depends upon the probability of SC between brain regions, with this dependence adhering to structural-functional links revealed by our fMRI and DTI data. We further characterize the functional hierarchy of functionally connected brain regions by defining an ascendancy measure that compares the marginal probabilities of elevated activity between regions. In addition, we describe topological properties of the network, which is composed of connected region pairs, by performing graph theoretic analyses. We demonstrate the use of our Bayesian model using fMRI and DTI data from a study of auditory processing. We further illustrate the advantages of our method by comparisons to methods that only incorporate functional information.

  8. Bonding in phase change materials: concepts and misconceptions

    Science.gov (United States)

    Jones, R. O.

    2018-04-01

    Bonding concepts originating in chemistry are surveyed from a condensed matter perspective, beginning around 1850 with ‘valence’ and the word ‘bond’ itself. The analysis of chemical data in the 19th century resulted in astonishing progress in understanding the connectivity and stereochemistry of molecules, almost without input from physicists until the development of quantum mechanics in 1925 and afterwards. The valence bond method popularized by Pauling and the molecular orbital methods of Hund, Mulliken, Bloch, and Hückel play major roles in the subsequent development, as does the central part played by the kinetic energy in covalent bonding (Ruedenberg and others). ‘Metallic’ (free electron) and related approaches, including pseudopotential and density functional theories, have been remarkably successful in understanding structures and bonding in molecules and solids. We discuss these concepts in the context of phase change materials, which involve the rapid and reversible transition between amorphous and crystalline states, and note the confusion that some have caused, in particular ‘resonance’ and ‘resonant bonding’.

  9. Copper wire bonding

    CERN Document Server

    Chauhan, Preeti S; Zhong, ZhaoWei; Pecht, Michael G

    2014-01-01

    This critical volume provides an in-depth presentation of copper wire bonding technologies, processes and equipment, along with the economic benefits and risks.  Due to the increasing cost of materials used to make electronic components, the electronics industry has been rapidly moving from high cost gold to significantly lower cost copper as a wire bonding material.  However, copper wire bonding has several process and reliability concerns due to its material properties.  Copper Wire Bonding book lays out the challenges involved in replacing gold with copper as a wire bond material, and includes the bonding process changes—bond force, electric flame off, current and ultrasonic energy optimization, and bonding tools and equipment changes for first and second bond formation.  In addition, the bond–pad metallurgies and the use of bare and palladium-coated copper wires on aluminum are presented, and gold, nickel and palladium surface finishes are discussed.  The book also discusses best practices and re...

  10. In silico approach to designing rational metagenomic libraries for functional studies.

    Science.gov (United States)

    Kusnezowa, Anna; Leichert, Lars I

    2017-05-22

    With the development of Next Generation Sequencing technologies, the number of predicted proteins from entire (meta-) genomes has risen exponentially. While for some of these sequences protein functions can be inferred from homology, an experimental characterization is still a requirement for the determination of protein function. However, functional characterization of proteins cannot keep pace with our capabilities to generate more and more sequence data. Here, we present an approach to reduce the number of proteins from entire (meta-) genomes to a reasonably small number for further experimental characterization without loss of important information. About 6.1 million predicted proteins from the Global Ocean Sampling Expedition Metagenome project were distributed into classes based either on homology to existing hidden markov models (HMMs) of known families, or de novo by assessment of pairwise similarity. 5.1 million of these proteins could be classified in this way, yielding 18,437 families. For 4,129 protein families, which did not match existing HMMs from databases, we could create novel HMMs. For each family, we then selected a representative protein, which showed the closest homology to all other proteins in this family. We then selected representatives of four families based on their homology to known and well-characterized lipases. From these four synthesized genes, we could obtain the novel esterase/lipase GOS54, validating our approach. Using an in silico approach, we were able improve the success rate of functional screening and make entire (meta-) genomes amenable for biochemical characterization.

  11. A note on the control function approach with an instrumental variable and a binary outcome.

    Science.gov (United States)

    Tchetgen Tchetgen, Eric J

    2014-12-01

    Unobserved confounding is a well known threat to causal inference in non-experimental studies. The instrumental variable design can under certain conditions be used to recover an unbiased estimator of a treatment effect even if unobserved confounding cannot be ruled out with certainty. For continuous outcomes, two stage least squares is the most common instrumental variable estimator used in epidemiologic applications. For a rare binary outcome, an analogous linear-logistic two-stage procedure can be used. Alternatively, a control function approach is sometimes used which entails entering the residual from the first stage linear model as a covariate in a second stage logistic regression of the outcome on the treatment. Both strategies for binary response have previously formally been justified only for continuous exposure, which has impeded widespread use of the approach outside of this setting. In this note, we consider the important setting of binary exposure in the context of a binary outcome. We provide an alternative motivation for the control function approach which is appropriate for binary exposure, thus establishing simple conditions under which the approach may be used for instrumental variable estimation when the outcome is rare. In the proposed approach, the first stage regression involves a logistic model of the exposure conditional on the instrumental variable, and the second stage regression is a logistic regression of the outcome on the exposure adjusting for the first stage residual. In the event of a non-rare outcome, we recommend replacing the second stage logistic model with a risk ratio regression.

  12. The Theoretical Approaches to Defining the Essence and Functions of Leasing

    Directory of Open Access Journals (Sweden)

    Levchenko Alexander A.

    2017-03-01

    Full Text Available The article is aimed at researching the theoretical foundations, generalizing scientific approaches to interpretation of the concept of «leasing», defining the main economic characteristics and functions of leasing. Scientific approaches of researchers to definition of the concept of «leasing» were systematized. New scientific approaches to interpretation of the concept of leasing as a form of public-private partnership, a form of ensuring competitiveness, have been allocated. The author’s own point of view on defining the economic essence of leasing as a special type of entrepreneurial activity which at the same time is implemented in the form of the credit-investment along with the trade-property relations has been substantiated. The main functions of leasing according to the object and subject approach in terms of outsourcing have been disclosed. Further researches in this direction will concern systematization of scientific approaches and definition of new attributes of the specific classification of leasing.

  13. Moral functioning: socio-psychological approach.Social intuitionist theory of John Haidt

    Directory of Open Access Journals (Sweden)

    Victor A. Zaikin

    2017-03-01

    Full Text Available The paper studies the methodological aspect of developing social intuitionist approach to moral psychology. The paper reveals the possibility of applying this approach to the study of morality and moral functioning today, emphasizes the representation of issues in moral psychology methodological origins of social psychology, both in Russia and abroad. Social and psychological foundations of social intuitionist approach are described in detail. The research results show that the child perceiving the concept of fairness and variability in the framework of a specific group membership is culturally determined. The matter of special consideration is the theory of the American social psychologist George Haidt. The results of his work and his colleagues’ works are presented herein describing the concept of cultural variable moral intuitions, the findings of empirical studies carried out in the framework of this approach are summarized. The paper reveals the fundamental provisions of the social and intuitionistic theory. The comparative analysis of the social intuitionistic and cognitive approaches in moral psychology is presented. The conclusion that the relativistic understanding of morality is not an obstacle to its study, and the presence of various determinants of moral functioning should be based on further empirical research. The authors conceptualized the current state of social intuitionistic theory of moral functioning, which describes the theoretical and methodological sources of this area (Rawls, 2010; Freud, 2005; Hume, 1996; Hare’s, 1981. As justification for this approach the paper considers the phenomena studied in psychology, social cognition, and those that create the possibility of developing this area, namely affective motivation (Zajonc, 1980, fair-world hypothesis (Lerner, 1965, the objectivity of the illusion (Perkins, Allen, & Hafner , 1983, the phenomenon of «naive realism» (Griffin, & Ross, 1991, group interaction in a

  14. Trochanteric osteotomy versus posterolateral approach: function the first year post surgery. A pilot study

    Directory of Open Access Journals (Sweden)

    van Biezen Frans C

    2011-06-01

    Full Text Available Abstract Background Although no prospective studies have compared functional results of trochanteric osteotomy and a non-trochanteric approach, most surgeons feel that trochanteric osteotomy is outdated in simple hip arthroplasty. Reasons not to perform an osteotomy include the fear of longer rehabilitation and worse (final functional outcome. Method This prospective study examines differences in rehabilitation between posterolateral and trochanteric approach one year post-surgery using questionnaires (WOMAC, SF-36, HHS and functional tests (walking, climbing stairs, rising from sitting, and strength tests. Of the 109 patients 24 had a trochanteric osteotomy: the selected approach was based on the surgeon's preference. The trochanteric osteotomy group included more patients with developmental dysplasia of the hip. Before the start of the study no power analysis was performed. Results Data from the questionnaires showed no significant differences between the two groups at 3, 6 and 12-months follow-up. At 3-months follow-up patients in the trochanteric osteotomy group scored lower on the functional tests. This difference had disappeared at 6 and 12-months follow-up, except for abduction force which remained lower in the trochanteric osteotomy group in patients with a non union of the TO. Conclusion For simple hip arthroplasty an approach without osteotomy seems a logical choice. Although the power of this study is low, in experienced hands trochanteric osteotomy seems to give good functional results at 6-12 months post surgery if trochanteric union is obtained. Therefore, one should not hesitate to perform an osteotomy in difficult cases.

  15. A Geometric Approach to Decouple Robotino Motions and its Functional Controllability

    Science.gov (United States)

    Straßberger, Daniel; Mercorelli, Paolo; Sergiyenko, Oleg

    2015-11-01

    This paper analyses a functional control of the Robotino. The proposed control strategy considers a functional decoupling control strategy realized using a geometric approach and the invertibility property of the DC-drives with which the Robotino is equipped. For a given control structure the functional controllability is proven for motion trajectories of class C3, continuous functions with third derivative also being continuous. Horizontal, Vertical and Angular motions are considered and the decoupling between these motions is obtained. Control simulation results using real data of the Robotino are shown. The used control which enables to produce the presented results is a standard Linear Model Predictive Control (LMPC), even though for sake of brevity the standard algorithm is not shown.

  16. Posterior Approach for Double Nerve Transfer for Restoration of Shoulder Function in Upper Brachial Plexus Palsy

    Science.gov (United States)

    Colbert, Stephen H.

    2006-01-01

    Restoration of shoulder function is one of the most critical goals of treatment of brachial plexus injuries. Primary repair or nerve grafting of avulsion injuries of the upper brachial plexus in adults often leads to poor recovery. Nerve transfers have provided an alternative treatment with great potential for improved return of function. Many different nerves have been utilized as donor nerves for transfer to the suprascapular nerve and axillary nerve for return of shoulder function with variable results. As our knowledge of shoulder neuromuscular anatomy and physiology improves and our experience with nerve transfers increases, so evolve the specific transfer procedures. This article presents a technique and rationale for reconstructing shoulder function by transferring the distal spinal accessory nerve to the suprascapular nerve and the nerve branch to the medial head of the triceps to the axillary nerve, both through a posterior approach. PMID:18780028

  17. Halogen Bonds in Novel Polyhalogen Monoanions.

    Science.gov (United States)

    Wang, Changwei; Danovich, David; Shaik, Sason; Mo, Yirong

    2017-06-27

    Polyhalogen monoanions [X 2n+1 ] - (X=Cl and Br; n=1, 2, 3, 4, and 5) have been systematically studied using the block-localized wave function (BLW) method, which offers a valence bond (VB) analysis. For each species, the most stable isomer can be described as a central halide anion X - non-classically bonded to a number of dihalogen molecules X 2 via "halogen bonds". VB analyses confirm the dominant role of the charge-transfer interaction between the lone pair on X - and the σ-anti-bonding orbital of X 2 molecule (n→σ*) in X 3 - and higher analogues. Thus, our study demonstrates that these halogen bonds are essentially dative covalent interactions. Importantly, the charge-transfer interaction between [X 2n-1 ] - and X 2 decreases with the increasing n, in accord with the weakening of the Lewis basicity as characterized by the corresponding HOMO energy. The reduction of the charge transfer interaction underscores the reduction of covalence in halogen bonds in [X 2n+1 ] - . This tendency highlights the anti-cooperative effect in polyhalogen monoanions. All in all, the halogen bond between X - and nX 2 molecules exhibits the same trends as in X - with a single X 2 molecule. In other words, halogen bonding in the larger clusters derives from the same bonding mechanism as the [X 3 ] - anion. As such, the X - ⋅⋅⋅X 2 halogen bond at different bond lengths forms a gauge of covalence for the entire [X 2n+1 ] - family. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Composite Laser Ceramics by Advanced Bonding Technology.

    Science.gov (United States)

    Ikesue, Akio; Aung, Yan Lin; Kamimura, Tomosumi; Honda, Sawao; Iwamoto, Yuji

    2018-02-09

    Composites obtained by bonding materials with the same crystal structure and different chemical compositions can create new functions that do not exist in conventional concepts. We have succeeded in bonding polycrystalline YAG and Nd:YAG ceramics without any interstices at the bonding interface, and the bonding state of this composite was at the atomic level, similar to the grain boundary structure in ceramics. The mechanical strength of the bonded composite reached 278 MPa, which was not less than the strength of each host material (269 and 255 MPa). Thermal conductivity of the composite was 12.3 W/mK (theoretical value) which is intermediate between the thermal conductivities of YAG and Nd:YAG (14.1 and 10.2 W/mK, respectively). Light scattering cannot be detected at the bonding interface of the ceramic composite by laser tomography. Since the scattering coefficients of the monolithic material and the composite material formed by bonding up to 15 layers of the same materials were both 0.10%/cm, there was no occurrence of light scattering due to the bonding. In addition, it was not detected that the optical distortion and non-uniformity of the refractive index variation were caused by the bonding. An excitation light source (LD = 808 nm) was collimated to 200 μm and irradiated into a commercial 1% Nd:YAG single crystal, but fracture damage occurred at a low damage threshold of 80 kW/cm². On the other hand, the same test was conducted on the bonded interface of 1% Nd:YAG-YAG composite ceramics fabricated in this study, but it was not damaged until the excitation density reached 127 kW/cm². 0.6% Nd:YAG-YAG composite ceramics showed high damage resistance (up to 223 kW/cm²). It was concluded that composites formed by bonding polycrystalline ceramics are ideal in terms of thermo-mechanical and optical properties.

  19. Penile sparing surgical approaches for primary penile tumors: preserving function and appearance.

    Science.gov (United States)

    Baumgarten, Adam S; Fisher, John S; Lawindy, Samuel M; Pavlinec, Jonathan G; Carrion, Rafael E; Spiess, Philippe E

    2017-10-01

    Penile cancer is a rare and potentially disfiguring disease. There are multiple treatment options for primary penile lesions. Penile sparing approaches offer an attractive option as they can provide several quality of life benefits without detrimental oncologic outcomes. With appropriate diagnostic evaluation and staging, penile sparing techniques provide proper cancer control with improved cosmetic and functional results. Regardless of the chosen treatment modality, a commitment to close follow-up remains a critical component of all treatment considerations. The goal of this review is to provide an overview of the multiple treatment strategies for primary penile tumors with a focus on penile sparing surgical approaches.

  20. A regularized clustering approach to brain parcellation from functional MRI data

    Science.gov (United States)

    Dillon, Keith; Wang, Yu-Ping

    2017-08-01

    We consider a data-driven approach for the subdivision of an individual subject's functional Magnetic Resonance Imaging (fMRI) scan into regions of interest, i.e., brain parcellation. The approach is based on a computational technique for calculating resolution from inverse problem theory, which we apply to neighborhood selection for brain connectivity networks. This can be efficiently calculated even for very large images, and explicitly incorporates regularization in the form of spatial smoothing and a noise cutoff. We demonstrate the reproducibility of the method on multiple scans of the same subjects, as well as the variations between subjects.

  1. The effect of ceramic primer on shear bond strength of resin composite cement to zirconia: a function of water storage and thermal cycling.

    Science.gov (United States)

    Keul, Christine; Liebermann, Anja; Roos, Malgorzata; Uhrenbacher, Julia; Stawarczyk, Bogna; Ing, Dipl

    2013-11-01

    The authors investigated the use of ceramic primers combined with self-adhesive resin composite cements on the shear bond strength (SBS) to zirconia and compared them with one conventional resin composite cement. The authors divided zirconia substrates (N = 550) into three groups: RelyX Unicem Aplicap self-adhesive universal resin composite cement (3M ESPE, St. Paul, Minn.) (group A) (n = 220); G-CEM Capsule self-adhesive resin composite cement (GC Europe, Leuven, Belgium) (group B) (n = 220); and Panavia 21 with Clearfil Porcelain Bond Activator and Clearfil SE Bond primer (n = 110) (Kuraray Dental, Tokyo) used as a standard comparison (SC). The authors examined the self-adhesive resin composite cements without (0) and with (1) the use of a ceramic primer. They measured SBS initially (37°C for three hours), after water storage (37°C for one, four, nine, 16 or 25 days) and after thermal cycling (5°C and 55°C for 1,500, 6,000, 13,500, 24,000 or 37,500 cycles). The authors analyzed data by using descriptive statistics, the Mann-Whitney test, the Kruskal-Wallis test and a χ(2) test. Application of a ceramic primer did not result in a negative impact on SBS. Specimens in the A1 group (that is, RelyX Unicem Aplicap with ceramic primer) exhibited significantly higher SBS before and after water storage and thermal cycling compared with specimens that were not treated with a primer. The self-adhesive resin composite cements combined with ceramic primer exhibited similar or higher SBS values compared with those in the SC group at each aging duration (that is, water storage and thermal cycling). With respect to G-CEM Capsule, the authors observed a significantly positive effect of the primer after nine and 16 days' water storage and after one and four days' thermal cycling. They observed predominantly adhesive failures. Ceramic primer in combination with self-adhesive resin composite cement demonstrated a positive effect on SBS to zirconia and should be used for

  2. Actor bonds after relationship dissolution

    DEFF Research Database (Denmark)

    Skaates, Maria Anne

    2000-01-01

    Most of the presented papers at the 1st NoRD Workshop can be classified as belonging to the business marketing approach to relationship dissolution. Two papers were conceptual, and the remaining six were empirical studies. The first conceptual study by Skaates (2000) focuses on the nature...... of the actor bonds that remain after a business relationship has ended. The study suggests that an interdisciplinary approach would provide a richer understanding of the phenomenon; this could be achieved by using e.g. Bourdieu's sociological concepts in dissolution research....

  3. Molecular docking, TG/DTA, molecular structure, harmonic vibrational frequencies, natural bond orbital and TD-DFT analysis of diphenyl carbonate by DFT approach

    Science.gov (United States)

    Xavier, S.; Periandy, S.; Carthigayan, K.; Sebastian, S.

    2016-12-01

    Vibrational spectral analysis of Diphenyl Carbonate (DPC) is carried out by using FT-IR and FT-Raman spectroscopic techniques. It is found that all vibrational modes are in the expected region. Gaussian computational calculations were performed using B3LYP method with 6-311++G (d, p) basis set. The computed geometric parameters are in good agreement with XRD data. The observation shows that the structure of the carbonate group is unsymmetrical by ∼5° due to the attachment of the two phenyl rings. The stability of the molecule arising from hyperconjugative interaction and charge delocalization are analyzed by Natural Bond Orbital (NBO) study and the results show the lone pair transition has higher stabilization energy compared to all other. The 1H and 13C NMR chemical shifts are calculated using the Gauge-Including Atomic Orbital (GIAO) method with B3LYP/6-311++G (d, p) method. The chemical shifts computed theoretically go very closer to the experimental results. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies and Molecular electrostatic potential (MEP) exhibit the high reactivity nature of the molecule. The non-linear optical property of the DPC molecule predicted theoretically found to be good candidate for NLO material. TG/DTA analysis was made and decomposition of the molecule with respect to the temperature was studied. DPC having the anthelmintic activity is docked in the Hemoglobin of Fasciola hepatica protein. The DPC has been screened to antimicrobial activity and found to exhibit antibacterial effects.

  4. Behavior of the E-E' Bonds (E, E' = S and Se) in Glutathione Disulfide and Derivatives Elucidated by Quantum Chemical Calculations with the Quantum Theory of Atoms-in-Molecules Approach.

    Science.gov (United States)

    Hayashi, Satoko; Tsubomoto, Yutaka; Nakanishi, Waro

    2018-02-17

    The nature of the E-E' bonds (E, E' = S and Se) in glutathione disulfide ( 1 ) and derivatives 2 - 3 , respectively, was elucidated by applying quantum theory of atoms-in-molecules (QTAIM) dual functional analysis (QTAIM-DFA), to clarify the basic contribution of E-E' in the biological redox process, such as the glutathione peroxidase process. Five most stable conformers a - e were obtained, after applying the Monte-Carlo method then structural optimizations. In QTAIM-DFA, total electron energy densities H b ( r c ) are plotted versus H b ( r c ) - V b ( r c )/2 at bond critical points (BCPs), where V b ( r c ) are potential energy densities at BCPs. Data from the fully optimized structures correspond to the static nature. Those containing perturbed structures around the fully optimized one in the plot represent the dynamic nature of interactions. The behavior of E-E' was examined carefully. Whereas E-E' in 1a - 3e were all predicted to have the weak covalent nature of the shared shell interactions, two different types of S-S were detected in 1 , depending on the conformational properties. Contributions from the intramolecular non-covalent interactions to stabilize the conformers were evaluated. An inverse relationship was observed between the stability of a conformer and the strength of E-E' in the conformer, of which reason was discussed.

  5. A DYNAMIC DENSITY FUNCTIONAL THEORY APPROACH TO DIFFUSION IN WHITE DWARFS AND NEUTRON STAR ENVELOPES

    Energy Technology Data Exchange (ETDEWEB)

    Diaw, A.; Murillo, M. S. [New Mexico Consortium, Los Alamos, NM 87544 (United States)

    2016-09-20

    We develop a multicomponent hydrodynamic model based on moments of the Born–Bogolyubov–Green–Kirkwood–Yvon hierarchy equations for physical conditions relevant to astrophysical plasmas. These equations incorporate strong correlations through a density functional theory closure, while transport enters through a relaxation approximation. This approach enables the introduction of Coulomb coupling correction terms into the standard Burgers equations. The diffusive currents for these strongly coupled plasmas is self-consistently derived. The settling of impurities and its impact on cooling can be greatly affected by strong Coulomb coupling, which we show can be quantified using the direct correlation function.

  6. Real-time functional integral approach to the quantum disordered spin systems

    International Nuclear Information System (INIS)

    Kopec, T.K.

    1989-01-01

    In this paper the effect of randomness and frustration in the quantum Ising spin glass in a transverse field is studied by using the thermofield dynamics (TFD), the real time, finite temperature quantum field theory. It is shown that the method can be conveniently used for the averaging of the free energy of the system by completely avoiding the use of the n-replica trick. The effective dynamic Lagrangian for the disorder averaged causal, correlations and response Green functions is derived by functional integral approach. Furthermore, the properties of this Lagrangian are analyzed by the saddle point method which leads to the self-consistent equation for the spin glass order parameter

  7. Quantum Numbers and the Eigenfunction Approach to Obtain Symmetry Adapted Functions for Discrete Symmetries

    Directory of Open Access Journals (Sweden)

    Renato Lemus

    2012-11-01

    Full Text Available The eigenfunction approach used for discrete symmetries is deduced from the concept of quantum numbers. We show that the irreducible representations (irreps associated with the eigenfunctions are indeed a shorthand notation for the set of eigenvalues of the class operators (character table. The need of a canonical chain of groups to establish a complete set of commuting operators is emphasized. This analysis allows us to establish in natural form the connection between the quantum numbers and the eigenfunction method proposed by J.Q. Chen to obtain symmetry adapted functions. We then proceed to present a friendly version of the eigenfunction method to project functions.

  8. Compressive modulus of adhesive bonded rubber block

    OpenAIRE

    Wiriya Thongruang; Charoenyut Dechwayukul

    2008-01-01

    The present study examined the effect of a thin adhesive layer on the modulus of an elastic rubber block bonded between two plates. The plates were assumed to be rigid, both in extension and flexure, and subjected to vertical compression loading. The Gent’s approach was used to obtain the analytic deformations of the rubber and adhesive. The analytic deformations were then validated with the finite element model. There was a good agreement between both methods. The modulus of the bonded rubbe...

  9. Towards Unconventional Applications of Wire Bonding

    OpenAIRE

    Schröder, Stephan

    2018-01-01

    This thesis presents novel heterogeneous integration approaches of wire materials to fabricated and package MEMS devices by exploring unconventional applications of wire bonding technology. Wire bonding, traditionally endemic in the realm of device packaging to establish electrical die-to-package interconnections, is an attractive back-end technology, offering promising features, such as high throughput, flexibility and placement accuracy. Exploiting the advantages of state-of-the-art wire bo...

  10. NARX prediction of some rare chaotic flows: Recurrent fuzzy functions approach

    International Nuclear Information System (INIS)

    Goudarzi, Sobhan; Jafari, Sajad; Moradi, Mohammad Hassan; Sprott, J.C.

    2016-01-01

    The nonlinear and dynamic accommodating capability of time domain models makes them a useful representation of chaotic time series for analysis, modeling and prediction. This paper is devoted to the modeling and prediction of chaotic time series with hidden attractors using a nonlinear autoregressive model with exogenous inputs (NARX) based on a novel recurrent fuzzy functions (RFFs) approach. Case studies of recently introduced chaotic systems with hidden attractors plus classical chaotic systems demonstrate that the proposed modeling methodology exhibits better prediction performance from different viewpoints (short term and long term) compared to some other existing methods. - Highlights: • A new method is proposed for prediction of chaotic time series. • This method is based on novel recurrent fuzzy functions (RFFs) approach. • Some rare chaotic flows are used as test systems. • The new method shows proper performance in short-term prediction. • It also shows proper performance in prediction of attractor's topology.

  11. NARX prediction of some rare chaotic flows: Recurrent fuzzy functions approach

    Energy Technology Data Exchange (ETDEWEB)

    Goudarzi, Sobhan [Biomedical Engineering Department, Amirkabir University of Technology, Tehran 15875-4413 (Iran, Islamic Republic of); Jafari, Sajad, E-mail: sajadjafari@aut.ac.ir [Biomedical Engineering Department, Amirkabir University of Technology, Tehran 15875-4413 (Iran, Islamic Republic of); Moradi, Mohammad Hassan [Biomedical Engineering Department, Amirkabir University of Technology, Tehran 15875-4413 (Iran, Islamic Republic of); Sprott, J.C. [Department of Physics, University of Wisconsin–Madison, Madison, WI 53706 (United States)

    2016-02-15

    The nonlinear and dynamic accommodating capability of time domain models makes them a useful representation of chaotic time series for analysis, modeling and prediction. This paper is devoted to the modeling and prediction of chaotic time series with hidden attractors using a nonlinear autoregressive model with exogenous inputs (NARX) based on a novel recurrent fuzzy functions (RFFs) approach. Case studies of recently introduced chaotic systems with hidden attractors plus classical chaotic systems demonstrate that the proposed modeling methodology exhibits better prediction performance from different viewpoints (short term and long term) compared to some other existing methods. - Highlights: • A new method is proposed for prediction of chaotic time series. • This method is based on novel recurrent fuzzy functions (RFFs) approach. • Some rare chaotic flows are used as test systems. • The new method shows proper performance in short-term prediction. • It also shows proper performance in prediction of attractor's topology.

  12. The Quality of Life and relevant Approaches based on Capabilities and Functionalities

    Directory of Open Access Journals (Sweden)

    Matei Șimandan

    2014-12-01

    Full Text Available Recent research regarding the quality of life developed different approaches concerning the use of objective and subjective indicators, as well as the relevance of hypotheses, propositions and methods of analysis or of evaluation. Starting from the conceptual difficulties regarding the term of ‘quality of life’, this article focuses upon the contributions of Amartya Sen on the relationships between resources, liberties, capabilities, functionalities and human development. A separate section attempts to capture the shift of accent from the approaches of a quantitative type towards those of a qualitative type, founded on capabilities, functionalities, and the factors of conversion of resources into elements of quality of subjective life. The following sections are consecrated to the contributions to the development of the model proposed by Amartya Sen and to the reception of this model by a few specialists in the field, as well as to its relevance within scientific research and the foundation of public policies.

  13. Control of a Biped Robot by Total Rate of Angular Momentum Using the Task Function Approach

    Directory of Open Access Journals (Sweden)

    J. A. Rojas-Estrada

    2005-01-01

    Full Text Available In this work we address the control problem of biped robots by using the task function approach. A problem arrives when one of the feet is in contact with the ground, which presents imperfections. There is then the possibility that the biped robot undergoes a fall. It is difficult to track any trajectory due to the presence of unevenness on the ground. What we propose is to use the task function approach combined with the application of the total rate of angular momentum to obtain a control law for the ankle. By this technique, the tracking becomes more smooth and the balance is assured. The control law proposed allows the upper part of the robot to be controlled independently since only the ankle actuators are concerned. We enounce the formal problem and present some simulations with real parameters of a 21 degrees of freedom biped robot.

  14. Resonating Valence Bond wavefunctions for electronic simulations

    Science.gov (United States)

    Sorella, Sandro

    2007-03-01

    We discuss several progress for the simulation of strongly correlated electrons, based on an efficient implementation of the Resonating Valence Bond (RVB) theory with Quantum Monte Carlo (QMC). Due to very important advances[1] in the energy optimization of strongly correlated variational wave functions, it is now possible to optimize several variational parameters with remarkable efficiency even within a stochastic approach such as QMC. In this way it is possible to describe very accurately the electronic correlation by a first principle many-body wave function, that can be extended to fairly large electronic systems. Indeed a remarkable improvement of the Hartree-Fock theory is provided by the so called RVB wave function introduced by P.W. Anderson in the context of High-Tc superconductivity[2]. For instance, by means of this paradigm, it has been possible to perform a realistic and accurate simulation of the benzene dimer, where we have found that the RVB correlation of the benzene ring plays a crucial role in the dimer bonding[3,4]. Finally we consider the still controversial low-temperature and high-pressure phase diagram of Hydrogen by using the same RVB wavefunction. We use a novel second order Langevin dynamics by introducing a consistent friction tensor, allowing to remain in thermal equilibrium even with very noisy forces, namely determined by QMC with very short runs. This allows us to simulate finite temperature systems (˜100 H) with very high efficiency, while the variational parameters are consistently optimized during the ionic dynamics. *[1] See C. J. Umrigar, J. Toulouse, C. Filippi, S. Sorella and R. G. Hennig, cond-mat/0611094 and references therein. *[2] P. W. Anderson Science 235, 1196 (1987). *[3] M. Casula, C. Attaccalite and S. Sorella J. Chem. Phys. 121 7110 (2004). *[4] S. Sorella, M. Casula and D. Rocca in preparation. *[5] C. Attaccalite and S. Sorella in preparation.

  15. Bonding and Molecular Geometry without Orbitals- The Electron Domain Model

    Science.gov (United States)

    Gillespie, Ronald J.; Spencer, James N.; Moog, Richard S.

    1996-07-01

    An alternative to the conventional valence bond approach to bonding and geometry-the electron domain model-is presented. This approach avoids some of the problems with the standard approach and presents fewer difficulties for the student, while still providing a physical basis for the VSEPR model and a link to the valence bond model. The electron domain model also emphasizes the importance of the Pauli principle in understanding the chemical bond and molecular geometry. A letter from Derek W. Smith in our April 2000 issue addresses the above.

  16. Atomically Bonded Transparent Superhydrophobic Coatings

    Energy Technology Data Exchange (ETDEWEB)

    Aytug, Tolga [ORNL

    2015-08-01

    Maintaining clarity and avoiding the accumulation of water and dirt on optically transparent surfaces such as US military vehicle windshields, viewports, periscope optical head windows, and electronic equipment cover glasses are critical to providing a high level of visibility, improved survivability, and much-needed safety for warfighters in the field. Through a combination of physical vapor deposition techniques and the exploitation of metastable phase separation in low-alkali borosilicate, a novel technology was developed for the fabrication of optically transparent, porous nanostructured silica thin film coatings that are strongly bonded to glass platforms. The nanotextured films, initially structurally superhydrophilic, exhibit superior superhydrophobicity, hence antisoiling ability, following a simple but robust modification in surface chemistry. The surfaces yield water droplet contact angles as high as 172°. Moreover, the nanostructured nature of these coatings provides increased light scattering in the UV regime and reduced reflectivity (i.e., enhanced transmission) over a broad range of the visible spectrum. In addition to these functionalities, the coatings exhibit superior mechanical resistance to abrasion and are thermally stable to temperatures approaching 500°C. The overall process technology relies on industry standard equipment and inherently scalable manufacturing processes and demands only nontoxic, naturally abundant, and inexpensive base materials. Such coatings, applied to the optical components of current and future combat equipment and military vehicles will provide a significant strategic advantage for warfighters. The inherent self-cleaning properties of such superhydrophobic coatings will also mitigate biofouling of optical windows exposed to high-humidity conditions and can help decrease repair/replacement costs, reduce maintenance, and increase readiness by limiting equipment downtime.

  17. Versatile and Resilient Hydrogen-Bonded Host Frameworks.

    Science.gov (United States)

    Adachi, Takuji; Ward, Michael D

    2016-12-20

    Low-density molecular host frameworks, whether equipped with persistent molecular-scale pores or virtual pores that are sustainable only when occupied by guest molecules, have emerged as a promising class of materials owing to the ability to tailor the size, geometry, and chemical character of their free space through the versatility of organic synthesis. As such, molecular frameworks are promising candidates for storage, separations of commodity and fine chemicals, heterogeneous catalysis, and optical and electronic materials. Frameworks assembled through hydrogen bonds, though generally not stable toward collapse in the absence of guests, promise significant chemical and structural diversity, with pores that can be tailored for a wide range of guest molecules. The utility of these frameworks, however, depends on the resilience of n-dimensional hydrogen-bonded motifs that serve as reliable building blocks so that the molecular constituents can be manipulated without disruption of the anticipated global solid-state architecture. Though many hydrogen-bonded frameworks have been reported, few exist that are amenable to systematic modification, thus limiting the design of functional materials. This Account reviews discoveries in our laboratory during the past decade related to a series of host frameworks based on guanidinium cations and interchangeable organosulfonate anions, in which the 3-fold symmetry and hydrogen-bonding complementarity of these ions prompt the formation of a two-dimensional (2-D) quasi-hexagonal hydrogen-bonding network that has proven to be remarkably resilient toward the introduction of a wide range of organic pendant groups attached to the sulfonate. Since an earlier report in this journal that focused primarily on organodisulfonate host frameworks with lamellar architectures, this unusually persistent network has afforded an unparalleled range of framework architectures and hundreds of new crystalline materials with predictable solid

  18. Factor Analysis vs. Fuzzy Sets Theory: Assessing the Influence of Different Techniques on Sen's Functioning Approach

    OpenAIRE

    Sara Lelli

    2001-01-01

    This paper explores a couple of specific operational interpretations of Sen's approach in view of assessing the extent to which the results originated by the implementation of Sen's concepts are influenced by the choice of the specific technique. By means of a survey based on a representative sample of Belgian individuals, seven achieved functioning's are identified via each technique and subsequently confronted. To structure the information and to facilitate comparisons, standard multivariat...

  19. Parenting approaches, family functionality, and internet addiction among Hong Kong adolescents

    OpenAIRE

    Wu, Cynthia Sau Ting; Wong, Ho Ting; Yu, Kin Fai; Fok, Ka Wing; Yeung, Sheung Man; Lam, Cheuk Ho; Liu, Ka Man

    2016-01-01

    Background Internet addiction (IA) among adolescents has become a global health problem, and public awareness of it is increasing. Many IA risk factors relate to parents and the family environment. This study examined the relationship between IA and parenting approaches and family functionality. Methods A cross-sectional study was conducted with 2021 secondary students to identify the prevalence of IA and to explore the association between adolescent IA and familial variables, including paren...

  20. A semi-analytical approach for solving of nonlinear systems of functional differential equations with delay

    Science.gov (United States)

    Rebenda, Josef; Šmarda, Zdeněk

    2017-07-01

    In the paper, we propose a correct and efficient semi-analytical approach to solve initial value problem for systems of functional differential equations with delay. The idea is to combine the method of steps and differential transformation method (DTM). In the latter, formulas for proportional arguments and nonlinear terms are used. An example of using this technique for a system with constant and proportional delays is presented.