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Sample records for bond selective chemistry

  1. Bond selective chemistry beyond the adiabatic approximation

    Energy Technology Data Exchange (ETDEWEB)

    Butler, L.J. [Univ. of Chicago, IL (United States)

    1993-12-01

    One of the most important challenges in chemistry is to develop predictive ability for the branching between energetically allowed chemical reaction pathways. Such predictive capability, coupled with a fundamental understanding of the important molecular interactions, is essential to the development and utilization of new fuels and the design of efficient combustion processes. Existing transition state and exact quantum theories successfully predict the branching between available product channels for systems in which each reaction coordinate can be adequately described by different paths along a single adiabatic potential energy surface. In particular, unimolecular dissociation following thermal, infrared multiphoton, or overtone excitation in the ground state yields a branching between energetically allowed product channels which can be successfully predicted by the application of statistical theories, i.e. the weakest bond breaks. (The predictions are particularly good for competing reactions in which when there is no saddle point along the reaction coordinates, as in simple bond fission reactions.) The predicted lack of bond selectivity results from the assumption of rapid internal vibrational energy redistribution and the implicit use of a single adiabatic Born-Oppenheimer potential energy surface for the reaction. However, the adiabatic approximation is not valid for the reaction of a wide variety of energetic materials and organic fuels; coupling between the electronic states of the reacting species play a a key role in determining the selectivity of the chemical reactions induced. The work described below investigated the central role played by coupling between electronic states in polyatomic molecules in determining the selective branching between energetically allowed fragmentation pathways in two key systems.

  2. Computational Chemistry of Adhesive Bonds

    Science.gov (United States)

    Phillips, Donald H.

    1999-01-01

    This investigation is intended to determine the electrical mechanical, and chemical properties of adhesive bonds at the molecular level. The initial determinations will be followed by investigations of the effects of environmental effects on the chemistry and properties of the bond layer.

  3. The dissociative chemisorption of water on Ni(111): Mode- and bond-selective chemistry on metal surfaces

    International Nuclear Information System (INIS)

    A fully quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of H2O, HOD, and D2O on Ni(111). For this late barrier system, excitation of both the bending and stretching modes significantly enhances dissociative sticking. The vibrational efficacies vary somewhat from mode-to-mode but are all relatively close to one, in contrast to methane dissociation, where the behavior is less statistical. Similar to methane dissociation, the motion of lattice atoms near the dissociating molecule can significantly modify the height of the barrier to dissociation, leading to a strong variation in dissociative sticking with substrate temperature. Given a rescaling of the barrier height, our results are in reasonable agreement with measurements of the dissociative sticking of D2O on Ni(111), for both laser-excited molecules with one or two quanta of excitation in the antisymmetric stretch and in the absence of laser excitation. Even without laser excitation, the beam contains vibrationally excited molecules populated at the experimental source temperature, and these make significant contributions to the sticking probability. At high collision energies, above the adiabatic barrier heights, our results correlate with these barrier heights and mode softening effects. At lower energies, dissociative sticking occurs primarily via vibrationally nonadiabatic pathways. We find a preference for O–H over O–D bond cleavage for ground state HOD molecules at all but the highest collision energies, and excitation of the O–H stretch gives close to 100% O–H selectivity at lower energies. Excitation of the O–D stretch gives a lower O–D cleavage selectivity, as the interaction with the surface leads to energy transfer from the O–D stretch into the O–H bond, when mode softening makes these vibrations nearly degenerate

  4. The dissociative chemisorption of water on Ni(111): Mode- and bond-selective chemistry on metal surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Farjamnia, Azar; Jackson, Bret, E-mail: jackson@chem.umass.edu [Department of Chemistry, University of Massachusetts, Amherst, Massachusetts 01003 (United States)

    2015-06-21

    A fully quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of H{sub 2}O, HOD, and D{sub 2}O on Ni(111). For this late barrier system, excitation of both the bending and stretching modes significantly enhances dissociative sticking. The vibrational efficacies vary somewhat from mode-to-mode but are all relatively close to one, in contrast to methane dissociation, where the behavior is less statistical. Similar to methane dissociation, the motion of lattice atoms near the dissociating molecule can significantly modify the height of the barrier to dissociation, leading to a strong variation in dissociative sticking with substrate temperature. Given a rescaling of the barrier height, our results are in reasonable agreement with measurements of the dissociative sticking of D{sub 2}O on Ni(111), for both laser-excited molecules with one or two quanta of excitation in the antisymmetric stretch and in the absence of laser excitation. Even without laser excitation, the beam contains vibrationally excited molecules populated at the experimental source temperature, and these make significant contributions to the sticking probability. At high collision energies, above the adiabatic barrier heights, our results correlate with these barrier heights and mode softening effects. At lower energies, dissociative sticking occurs primarily via vibrationally nonadiabatic pathways. We find a preference for O–H over O–D bond cleavage for ground state HOD molecules at all but the highest collision energies, and excitation of the O–H stretch gives close to 100% O–H selectivity at lower energies. Excitation of the O–D stretch gives a lower O–D cleavage selectivity, as the interaction with the surface leads to energy transfer from the O–D stretch into the O–H bond, when mode softening makes these vibrations nearly degenerate.

  5. Bonding, structure and solid-state chemistry

    CERN Document Server

    Ladd, Mark

    2016-01-01

    This book is aimed at undergraduate students in both chemistry and those degree subjects in which chemistry forms a significant part. It does not reflect any particular academic year, and so finds a place during the normal span of degree studies in the physical sciences. An A-level standard in science and mathematics is presumed; additional mathematical treatments are discussed in Appendices. An introductory first chapter leads into the main subject matter, which is treated through four chapters in terms of the principle bonding forces of cohesion in the solid state; a further chapter discusses nanosize materials. Important applications of the study topics are interspersed at appropriate points within the text. Each chapter is provided with a set of problems of varying degrees of difficulty, so as to assist the reader in gaining a facility with the subject matter and its applications. The problems are supplemented by detailed tutorial solutions, some of which present additional relevant material that indicate...

  6. Discovering Chemistry With Natural Bond Orbitals

    CERN Document Server

    Weinhold, Frank

    2012-01-01

    This book explores chemical bonds, their intrinsic energies, and the corresponding dissociation energies which are relevant in reactivity problems. It offers the first book on conceptual quantum chemistry, a key area for understanding chemical principles and predicting chemical properties. It presents NBO mathematical algorithms embedded in a well-tested and widely used computer program (currently, NBO 5.9). While encouraging a "look under the hood" (Appendix A), this book mainly enables students to gain proficiency in using the NBO program to re-express complex wavefunctions in terms of intui

  7. The CH/π hydrogen bond: Implication in chemistry

    Science.gov (United States)

    Nishio, M.

    2012-06-01

    The CH/π hydrogen bond is the weakest extreme of hydrogen bonds that occurs between a soft acid CH and a soft base π-system. Implication in chemistry of the CH/π hydrogen bond includes issues of conformation, crystal packing, and specificity in host/guest complexes. The result obtained by analyzing the Cambridge Structural Database is reviewed. The peculiar axial preference of isopropyl group in α-phellandrene and folded conformation of levopimaric acid have been explained in terms of the CH/π hydrogen bond, by high-level ab initio MO calculations. Implication of the CH/π hydrogen bond in structural biology is also discussed, briefly.

  8. Bond additivity corrections for quantum chemistry methods

    Energy Technology Data Exchange (ETDEWEB)

    C. F. Melius; M. D. Allendorf

    1999-04-01

    In the 1980's, the authors developed a bond-additivity correction procedure for quantum chemical calculations called BAC-MP4, which has proven reliable in calculating the thermochemical properties of molecular species, including radicals as well as stable closed-shell species. New Bond Additivity Correction (BAC) methods have been developed for the G2 method, BAC-G2, as well as for a hybrid DFT/MP2 method, BAC-Hybrid. These BAC methods use a new form of BAC corrections, involving atomic, molecular, and bond-wise additive terms. These terms enable one to treat positive and negative ions as well as neutrals. The BAC-G2 method reduces errors in the G2 method due to nearest-neighbor bonds. The parameters within the BAC-G2 method only depend on atom types. Thus the BAC-G2 method can be used to determine the parameters needed by BAC methods involving lower levels of theory, such as BAC-Hybrid and BAC-MP4. The BAC-Hybrid method should scale well for large molecules. The BAC-Hybrid method uses the differences between the DFT and MP2 as an indicator of the method's accuracy, while the BAC-G2 method uses its internal methods (G1 and G2MP2) to provide an indicator of its accuracy. Indications of the average error as well as worst cases are provided for each of the BAC methods.

  9. Computational Tools To Model Halogen Bonds in Medicinal Chemistry.

    Science.gov (United States)

    Ford, Melissa Coates; Ho, P Shing

    2016-03-10

    The use of halogens in therapeutics dates back to the earliest days of medicine when seaweed was used as a source of iodine to treat goiters. The incorporation of halogens to improve the potency of drugs is now fairly standard in medicinal chemistry. In the past decade, halogens have been recognized as direct participants in defining the affinity of inhibitors through a noncovalent interaction called the halogen bond or X-bond. Incorporating X-bonding into structure-based drug design requires computational models for the anisotropic distribution of charge and the nonspherical shape of halogens, which lead to their highly directional geometries and stabilizing energies. We review here current successes and challenges in developing computational methods to introduce X-bonding into lead compound discovery and optimization during drug development. This fast-growing field will push further development of more accurate and efficient computational tools to accelerate the exploitation of halogens in medicinal chemistry.

  10. Development and application of bond cleavage reactions in bioorthogonal chemistry.

    Science.gov (United States)

    Li, Jie; Chen, Peng R

    2016-03-01

    Bioorthogonal chemical reactions are a thriving area of chemical research in recent years as an unprecedented technique to dissect native biological processes through chemistry-enabled strategies. However, current concepts of bioorthogonal chemistry have largely centered on 'bond formation' reactions between two mutually reactive bioorthogonal handles. Recently, in a reverse strategy, a collection of 'bond cleavage' reactions has emerged with excellent biocompatibility. These reactions have expanded our bioorthogonal chemistry repertoire, enabling an array of exciting new biological applications that range from the chemically controlled spatial and temporal activation of intracellular proteins and small-molecule drugs to the direct manipulation of intact cells under physiological conditions. Here we highlight the development and applications of these bioorthogonal cleavage reactions. Furthermore, we lay out challenges and propose future directions along this appealing avenue of research.

  11. New Research Center Will Free Chemistry from Earth's Bonds

    Science.gov (United States)

    2008-10-01

    A new research center combining the tools of chemistry and astronomy will use the unique laboratory of interstellar space to free the study of basic chemistry from the restrictive bonds of Earth. The Center for Chemistry of the Universe will allow scientists to explore new types of chemical reactions that occur under the extreme conditions of space. The center will combine laboratory experiments, theoretical studies, and radio-telescope observations to dramatically expand our understanding of the processes that build molecules that may "seed" young planets with the building blocks of life. Astrochemistry Graphic CREDIT: Bill Saxton, NRAO/AUI/NSF The Center forges a unique research collaboration among leading scientists in the field of astrochemistry from the University of Arizona, The Ohio State University, the Harvard-Smithsonian Center for Astrophysics, the National Institute of Standards and Technology, the National Radio Astronomy Observatory, and a group of chemists and physicists at the University of Virginia engaged in research to understand the fundamentals of chemical reactions. "We hope to answer some very basic questions, such as just how did the molecules that ultimately became us get their start?" said Brooks Pate, Professor of Chemistry at the University of Virginia (UVa) and leader of the team that will form the new center. The team received an initial grant of 1.5 million from the National Science Foundation (NSF) to form the center during the next two years. If the NSF then fully approves the initiative, the foundation will provide funding of 4 million per year for up to ten years. The new center will bring together laboratory researchers, theoreticians, and observers using radio telescopes of the National Radio Astronomy Observatory (NRAO) and the Arizona Radio Observatory (ARO). The group of chemists participating in the center have discovered more than half of the new interstellar molecules identified worldwide in the past 18 months. The NRAO

  12. The EPOS Automated Selective Chemistry Analyzer evaluated.

    Science.gov (United States)

    Moses, G C; Lightle, G O; Tuckerman, J F; Henderson, A R

    1986-01-01

    We evaluated the analytical performance of the EPOS (Eppendorf Patient Oriented System) Automated Selective Chemistry Analyzer, using the following tests for serum analytes: alanine and aspartate aminotransferases, lactate dehydrogenase, creatine kinase, gamma-glutamyltransferase, alkaline phosphatase, and glucose. Results from the EPOS correlated well with those from comparison instruments (r greater than or equal to 0.990). Precision and linearity limits were excellent for all tests; linearity of the optical and pipetting systems was satisfactory. Reagent carryover was negligible. Sample-to-sample carryover was less than 1% for all tests, but only lactate dehydrogenase was less than the manufacturer's specified 0.5%. Volumes aspirated and dispensed by the sample and reagent II pipetting systems differed significantly from preset values, especially at lower settings; the reagent I system was satisfactory at all volumes tested. Minimal daily maintenance and an external data-reduction system make the EPOS a practical alternative to other bench-top chemistry analyzers.

  13. Enhancing prospective chemistry teachers cognitive structures in the topics of bonding and hybridization by internet-assisted chemistry applications

    Directory of Open Access Journals (Sweden)

    Özge Özyalçın Oskay, Sinem Dinçol

    2011-08-01

    Full Text Available The purpose of this study is to determine the effects of internet-assisted chemistry applications on prospective chemistry teachers’ cognitive structures in the topics of bonding and hybridization. The sample of the study consisted of 36 prospective chemistry teachers attending Hacettepe University, Faculty of Education, the Department of Chemistry Education in 2010-2011 academic year and taking Basic Chemistry I lesson. In the study, students were separated into experimental and control groups according to their pre-cognitive structures. Students were requested to answer two open ended questions. Answers by each student were gathered and evaluated by flow map method. “Bonding and hybridization” topics were taught to control group with traditional teaching method and to experimental group besides traditional method internet-assisted applications were conducted. The same open-ended questions were given to both groups and their cognitive structures were examined once more. The differences between control and experimental groups’ cognitive structures were examined. A significant difference was identified in favour of experimental group (p<0, 05. The mean score of the Experimental group was X=19.94, and the mean score of the Control group was X=13.88. In addition, subsequent to internet assisted chemistry applications differences in terms of concepts and descriptions in prospective chemistry teachers’ in experimental and control group cognitive structure have been determined. When post flow maps of prospective chemistry teachers in experimental group, on whom internet assisted chemistry applications were made, are formed, it has been determined that there are more statements about hybridization, hybridization types, molecule geometry and bond angles compared to control grou

  14. Valence-Bond Concepts in Coordination Chemistry and the Nature of Metal-Metal Bonds.

    Science.gov (United States)

    Pauling, Linus; Herman, Zelek S.

    1984-01-01

    Discusses the valence-bond method, applying it to some coordination compounds of metals, especially those involving metal-metal bonds. Suggests that transition metals can form as many as nine covalent bonds, permitting valence-theory to be extended to transition metal compounds in a more effective way than has been possible before. (JN)

  15. Two-Center/Three-Electron Sigma Half-Bonds in Main Group and Transition Metal Chemistry.

    Science.gov (United States)

    Berry, John F

    2016-01-19

    First proposed in a classic Linus Pauling paper, the two-center/three-electron (2c/3e) σ half-bond challenges the extremes of what may or may not be considered a chemical bond. Two electrons occupying a σ bonding orbital and one electron occupying the antibonding σ* orbital results in bond orders of ∼0.5 that are characteristic of metastable and exotic species, epitomized in the fleetingly stable He2(+) ion. In this Account, I describe the use of coordination chemistry to stabilize such fugacious three-electron bonded species at disparate ends of the periodic table. A recent emphasis in the chemistry of metal-metal bonds has been to prepare compounds with extremely short metal-metal distances and high metal-metal bond orders. But similar chemistry can be used to explore metal-metal bond orders less than one, including 2c/3e half-bonds. Bimetallic compounds in the Ni2(II,III) and Pd2(II,III) oxidation states were originally examined in the 1980s, but the evidence collected at that time suggested that they did not contain 2c/3e σ bonds. Both classes of compounds have been re-examined using EPR spectroscopy and modern computational methods that show the unpaired electron of each compound to occupy a M-M σ* orbital, consistent with 2c/3e Ni-Ni and Pd-Pd σ half-bonds. Elsewhere on the periodic table, a seemingly unrelated compound containing a trigonal bipyramidal Cu3S2 core caused a stir, leaving prominent theorists at odds with one another as to whether the compound contains a S-S bond. Due to my previous experience with 2c/3e metal-metal bonds, I suggested that the Cu3S2 compound could contain a 2c/3e S-S σ half-bond in the previously unknown oxidation state of S2(3-). By use of the Cambridge Database, a number of other known compounds were identified as potentially containing S2(3-) ligands, including a noteworthy set of cyclopentadienyl-supported compounds possessing diamond-shaped Ni2E2 units with E = S, Se, and Te. These compounds were subjected to

  16. A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms

    OpenAIRE

    Sarwar, G.; J. Godowitch; B. H. Henderson; K. Fahey; Pouliot, G.; W. T. Hutzell; Mathur, R.; Kang, D.; Goliff, W. S.; Stockwell, W. R.

    2013-01-01

    We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2) into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU). Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyace...

  17. A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms

    OpenAIRE

    Sarwar, G.; J. Godowitch; Henderson, B.; K. Fahey; Pouliot, G.; W. T. Hutzell; Mathur, R.; Kang, D.; Goliff, W. S.; Stockwell, W. R.

    2013-01-01

    We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2) into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU). Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, pe...

  18. Generalized Approach for Selecting Plasma Chemistries in Metal Etch

    OpenAIRE

    Chen, Kun-Chieh

    2016-01-01

    In this work, a generalized methodology, combining thermodynamic assessment of various etching chemistries and kinetic verification of etching efficacy, is proposed. To screen various chemistries, reactions between the dominant vapor phase/condensed species at various partial pressures of reactants are first considered. The volatility of etch product is determined to aid the selection of viable etch chemistry. Magnetic tunnel junction (MTJ) based magnetic random access memory (MRAM) was chose...

  19. Spatially Selective Functionalization of Conducting Polymers by "Electroclick" Chemistry

    DEFF Research Database (Denmark)

    Hansen, Thomas Steen; Daugaard, Anders Egede; Hvilsted, Søren;

    2009-01-01

    Conducting polymer microelectrodes can electrochemically generate the catalyst required for their own functionalization by "click chemistry" with high spatial resolution. Interdigitated microelectrodes prepared from an azide-containing conducting polymer are selectively functionalized in sequence...

  20. Selective host molecules obtained by dynamic adaptive chemistry.

    Science.gov (United States)

    Matache, Mihaela; Bogdan, Elena; Hădade, Niculina D

    2014-02-17

    Up till 20 years ago, in order to endow molecules with function there were two mainstream lines of thought. One was to rationally design the positioning of chemical functionalities within candidate molecules, followed by an iterative synthesis-optimization process. The second was the use of a "brutal force" approach of combinatorial chemistry coupled with advanced screening for function. Although both methods provided important results, "rational design" often resulted in time-consuming efforts of modeling and synthesis only to find that the candidate molecule was not performing the designed job. "Combinatorial chemistry" suffered from a fundamental limitation related to the focusing of the libraries employed, often using lead compounds that limit its scope. Dynamic constitutional chemistry has developed as a combination of the two approaches above. Through the rational use of reversible chemical bonds together with a large plethora of precursor libraries, one is now able to build functional structures, ranging from quite simple molecules up to large polymeric structures. Thus, by introduction of the dynamic component within the molecular recognition processes, a new perspective of deciphering the world of the molecular events has aroused together with a new field of chemistry. Since its birth dynamic constitutional chemistry has continuously gained attention, in particular due to its ability to easily create from scratch outstanding molecular structures as well as the addition of adaptive features. The fundamental concepts defining the dynamic constitutional chemistry have been continuously extended to currently place it at the intersection between the supramolecular chemistry and newly defined adaptive chemistry, a pivotal feature towards evolutive chemistry.

  1. Theoretical Chemistry Study of the Hydrogen-bonded Interaction between Acylamine and Chloromethane Compounds

    Institute of Scientific and Technical Information of China (English)

    GE Qing-Yu; WANG Hai-Jun; CHEN Jian-Hua

    2005-01-01

    The hydrogen-bonded interaction between acylamine and chloromethane was studied using theoretical calculation methods. Looking the interaction system as a hydrogen-bonded complex, the geometric optimization of the interaction system was performed with HF and B3LYP methods at 6-311++G** level. Stable structures of these complexes were obtained. Binding energies and some other physical chemistry parameters of them were computed and compared. According to the calculation results, it can be identified that DMA (DMF or DEF) can form stable complex with chloromethane by the hydrogen-bonded interaction between them. The stable orders of these hydrogen-bonded complexes were obtained and described as: DMF-CHCl3>DMF-CH2Cl2>DMF-CH3Cl, DEF-CHCl3>DEF-CH2Cl2>DEF-CH3Cl, DMA-CHCl3>DMA-CH2Cl2>DMA-CH3Cl, respectively.

  2. Site-selective and stereoselective functionalization of unactivated C–H bonds

    Science.gov (United States)

    Liao, Kuangbiao; Negretti, Solymar; Musaev, Djamaladdin G.; Bacsa, John; Davies, Huw M. L.

    2016-05-01

    The laboratory synthesis of complex organic molecules relies heavily on the introduction and manipulation of functional groups, such as carbon–oxygen or carbon–halogen bonds; carbon–hydrogen bonds are far less reactive and harder to functionalize selectively. The idea of C–H functionalization, in which C–H bonds are modified at will instead of the functional groups, represents a paradigm shift in the standard logic of organic synthesis. For this approach to be generally useful, effective strategies for site-selective C–H functionalization need to be developed. The most practical solutions to the site-selectivity problem rely on either intramolecular reactions or the use of directing groups within the substrate. A challenging, but potentially more flexible approach, would be to use catalyst control to determine which site in a particular substrate would be functionalized. Here we describe the use of dirhodium catalysts to achieve highly site-selective, diastereoselective and enantioselective C–H functionalization of n-alkanes and terminally substituted n-alkyl compounds. The reactions proceed in high yield, and functional groups such as halides, silanes and esters are compatible with this chemistry. These studies demonstrate that high site selectivity is possible in C–H functionalization reactions without the need for a directing or anchoring group present in the molecule.

  3. Two-dimensional gold nanostructures with high activity for selective oxidation of carbon–hydrogen bonds

    KAUST Repository

    Wang, Liang

    2015-04-22

    Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold–gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon–hydrogen bonds with molecular oxygen.

  4. Selective breaking of bonds in water with intense, 2-cycle, infrared laser pulses

    Energy Technology Data Exchange (ETDEWEB)

    Mathur, D., E-mail: atmol1@tifr.res.in; Dharmadhikari, A. K. [Tata Institute of Fundamental Research, 1 Homi Bhabha Road, Mumbai 400 005 (India); Dota, K. [Tata Institute of Fundamental Research, 1 Homi Bhabha Road, Mumbai 400 005 (India); Centre for Atomic and Molecular Physics, Manipal University, Manipal 576 104 (India); Dey, D.; Tiwari, A. K. [Indian Institute of Science Education and Research Kolkata, Mohanpur 741 246 (India); Dharmadhikari, J. A. [Centre for Atomic and Molecular Physics, Manipal University, Manipal 576 104 (India); De, S. [Saha Institute of Nuclear Physics, Bidhan Nagar, Kolkata 700 064 (India); Vasa, P. [Department of Physics, Indian Institute of Technology Bombay, Mumbai 400 076 (India)

    2015-12-28

    One of the holy grails of contemporary science has been to establish the possibility of preferentially breaking one of several bonds in a molecule. For instance, the two O–H bonds in water are equivalent: given sufficient energy, either one of them is equally likely to break. We report bond-selective molecular fragmentation upon application of intense, 2-cycle pulses of 800 nm laser light: we demonstrate up to three-fold enhancement for preferential bond breaking in isotopically substituted water (HOD). Our experimental observations are rationalized by means of ab initio computations of the potential energy surfaces of HOD, HOD{sup +}, and HOD{sup 2+} and explorations of the dissociation limits resulting from either O–H or O–D bond rupture. The observations we report present a formidable theoretical challenge that need to be taken up in order to gain insights into molecular dynamics, strong field physics, chemical physics, non-adiabatic processes, mass spectrometry, and time-dependent quantum chemistry.

  5. Selective breaking of bonds in water with intense, 2-cycle, infrared laser pulses

    Science.gov (United States)

    Mathur, D.; Dota, K.; Dey, D.; Tiwari, A. K.; Dharmadhikari, J. A.; Dharmadhikari, A. K.; De, S.; Vasa, P.

    2015-12-01

    One of the holy grails of contemporary science has been to establish the possibility of preferentially breaking one of several bonds in a molecule. For instance, the two O-H bonds in water are equivalent: given sufficient energy, either one of them is equally likely to break. We report bond-selective molecular fragmentation upon application of intense, 2-cycle pulses of 800 nm laser light: we demonstrate up to three-fold enhancement for preferential bond breaking in isotopically substituted water (HOD). Our experimental observations are rationalized by means of ab initio computations of the potential energy surfaces of HOD, HOD+, and HOD2+ and explorations of the dissociation limits resulting from either O-H or O-D bond rupture. The observations we report present a formidable theoretical challenge that need to be taken up in order to gain insights into molecular dynamics, strong field physics, chemical physics, non-adiabatic processes, mass spectrometry, and time-dependent quantum chemistry.

  6. Selective breaking of bonds in water with intense, 2-cycle, infrared laser pulses

    International Nuclear Information System (INIS)

    One of the holy grails of contemporary science has been to establish the possibility of preferentially breaking one of several bonds in a molecule. For instance, the two O–H bonds in water are equivalent: given sufficient energy, either one of them is equally likely to break. We report bond-selective molecular fragmentation upon application of intense, 2-cycle pulses of 800 nm laser light: we demonstrate up to three-fold enhancement for preferential bond breaking in isotopically substituted water (HOD). Our experimental observations are rationalized by means of ab initio computations of the potential energy surfaces of HOD, HOD+, and HOD2+ and explorations of the dissociation limits resulting from either O–H or O–D bond rupture. The observations we report present a formidable theoretical challenge that need to be taken up in order to gain insights into molecular dynamics, strong field physics, chemical physics, non-adiabatic processes, mass spectrometry, and time-dependent quantum chemistry

  7. Selective breaking of bonds in water with intense, 2-cycle, infrared laser pulses.

    Science.gov (United States)

    Mathur, D; Dota, K; Dey, D; Tiwari, A K; Dharmadhikari, J A; Dharmadhikari, A K; De, S; Vasa, P

    2015-12-28

    One of the holy grails of contemporary science has been to establish the possibility of preferentially breaking one of several bonds in a molecule. For instance, the two O-H bonds in water are equivalent: given sufficient energy, either one of them is equally likely to break. We report bond-selective molecular fragmentation upon application of intense, 2-cycle pulses of 800 nm laser light: we demonstrate up to three-fold enhancement for preferential bond breaking in isotopically substituted water (HOD). Our experimental observations are rationalized by means of ab initio computations of the potential energy surfaces of HOD, HOD(+), and HOD(2+) and explorations of the dissociation limits resulting from either O-H or O-D bond rupture. The observations we report present a formidable theoretical challenge that need to be taken up in order to gain insights into molecular dynamics, strong field physics, chemical physics, non-adiabatic processes, mass spectrometry, and time-dependent quantum chemistry.

  8. Supramolecular chemistry-general principles and selected examples from anion recognition and metallosupramolecular chemistry.

    Science.gov (United States)

    Albrecht, Markus

    2007-12-01

    This review gives an introduction into supramolecular chemistry describing in the first part general principles, focusing on terms like noncovalent interaction, molecular recognition, self-assembly, and supramolecular function. In the second part those will be illustrated by simple examples from our laboratories. Supramolecular chemistry is the science that bridges the gap between the world of molecules and nanotechnology. In supramolecular chemistry noncovalent interactions occur between molecular building blocks, which by molecular recognition and self-assembly form (functional) supramolecular entities. It is also termed the "chemistry of the noncovalent bond." Molecular recognition is based on geometrical complementarity based on the "key-and-lock" principle with nonshape-dependent effects, e.g., solvatization, being also highly influential. Self-assembly leads to the formation of well-defined aggregates. Hereby the overall structure of the target ensemble is controlled by the symmetry features of the certain building blocks. Finally, the aggregates can possess special properties or supramolecular functions, which are only found in the ensemble but not in the participating molecules. This review gives an introduction on supramolecular chemistry and illustrates the fundamental principles by recent examples from our group.

  9. Two-pulse laser control of bond-selective fragmentation

    DEFF Research Database (Denmark)

    Amstrup, Bjarne; Henriksen, Niels Engholm

    1996-01-01

    We elaborate on a two-pulse (pump-pump) laser control scheme for selective bond-breaking in molecules [Amstrup and Henriksen, J. Chem. Phys. 97, 8285 (1992)]. We show, in particular, that with this scheme one can overcome the obstacle of intramolecular vibrational relaxation. As an example, we...... be obtained when such a non-stationary vibrating ozone molecule is photodissociated with short laser pulses (similar to 10-15 fs) with a time delay corresponding to half a vibrational period (similar to 17 fs). (C) 1996 American Institute of Physics....

  10. Spectroscopic examinations of hydrogen bonding in hydroxy-functionalized ADMET chemistry.

    Science.gov (United States)

    Thompson, Donovan L; Wagener, Kenneth B; Schulze, Ulrich; Voit, Brigitte; Jehnichen, Dieter; Malanin, Mikhail

    2015-01-01

    Wide-angle X-ray scattering (WAXS) and temperature-dependent Fourier transform infrared spectroscopy (FTIR) spectroscopy are used to study hydrogen bonding interactions of a hydroxyl-functionalized polyethylene (PE) prepared by acyclic diene metathesis (ADMET) chemistry. The hydroxyl polymer exhibits an orthorhombic unit cell structure with characteristic reflection planes at (110) and (200), comparable to pure crystalline PE. These data unequivocally demonstrate that the OH branch is excluded from the PE lamellae. Furthermore, the polymer melts 100 °C higher than all previous analogous polymers possessing precision placed long aliphatic branches that also are excluded from PE lamellae. Temperature-dependent FTIR spectroscopy from ambient to 150 °C, followed by cooling to 125 °C supports exclusion of the hydroxyl group from the crystalline lattice. It is concluded that these hydroxyl groups form stable physical networks in the amorphous region via hydrogen bonding and are important for the overall morphology of such polymers. PMID:25393938

  11. Chemistry of zerumbone. 2. Regulation of ring bond cleavage and unique antibacterial activities of zerumbone derivatives.

    Science.gov (United States)

    Kitayama, T; Yamamoto, K; Utsumi, R; Takatani, M; Hill, R K; Kawai, Y; Sawada, S; Okamoto, T

    2001-10-01

    Further investigation of the chemistry of the eleven-membered cyclic sesquiterpene, zerumbone, the major component of the wild ginger, Zingiber zerumbet Smith, has revealed a new selective epoxidation process, a further example of a novel Favorskii-initiated double ring contraction, and a regiospecific fragmentation of zerumbone dibromide derivatives. Several zerumbone derivatives were found to be selective inhibitors of the growth of gram-positive bacteria. PMID:11758909

  12. A HYDROGEN BONDING ASSISTED CATALYST SCREENED OUT VIA COMBINATORIAL CHEMISTRY STRATEGY

    Institute of Scientific and Technical Information of China (English)

    XUMancai; OUZhize; 等

    2000-01-01

    Possibilities for enhancement of catalytic reaction rate by combining phase transfer catalysis and hydrogen bonding of the catalyst with the substrate and reagent were studied.A phase transfer catalyst library with sixty polystyrene-supported quaternary ammonium salt catalysts was synthesized.The reduction of acetophenone by NaBH4 was used as the probing reaction to select out the ost active catalyst in the library by using iterative method.which was the gel-type triethanolamine aminsating strongly asic anion exchange resin with the crosslinking degeree of 2% A hydrogen bonding assisted catalytic mechanism was proposed to explain the high catalytic activity of the catalyst.

  13. From ab initio quantum chemistry to molecular dynamics: The delicate case of hydrogen bonding in ammonia

    CERN Document Server

    Boese, A D; Martin, J M L; Marx, D; Chandra, Amalendu; Martin, Jan M.L.; Marx, Dominik

    2003-01-01

    The ammonia dimer (NH3)2 has been investigated using high--level ab initio quantum chemistry methods and density functional theory (DFT). The structure and energetics of important isomers is obtained to unprecedented accuracy without resorting to experiment. The global minimum of eclipsed C_s symmetry is characterized by a significantly bent hydrogen bond which deviates from linearity by about 20 degrees. In addition, the so-called cyclic C_{2h} structure is extremely close in energy on an overall flat potential energy surface. It is demonstrated that none of the currently available (GGA, meta--GGA, and hybrid) density functionals satisfactorily describe the structure and relative energies of this nonlinear hydrogen bond. We present a novel density functional, HCTH/407+, designed to describe this sort of hydrogen bond quantitatively on the level of the dimer, contrary to e.g. the widely used BLYP functional. This improved functional is employed in Car-Parrinello ab initio molecular dynamics simulations of liq...

  14. Bond-selective photodissociation caused by vibrational excitation

    International Nuclear Information System (INIS)

    Ultraviolet photodissociations of partially deuterated water (HOD) and ammonia (NHD2/NH2D) molecules excited to the vibrationally excited states have been investigated by using a crossed laser and molecular beams method. Branching ratio between the H- and D-atom ejection channels has been determined by utilizing a (2+1) resonance enhanced multiphoton ionization scheme of H and D atoms. For 243 nm photolysis of HOD in the 5νOD state, the OD bond dissociation has been solely observed with the branching ratio ,,(D+OH)/ ,,(H+OD) >12, which has been determined by the detection limit for the H atom. For the photolysis of NHD2/NH2D in the vibrationally excited states, the branching ratio between the NH and ND dissociation channels has been largely altered by the vibrational state selection. (author)

  15. Selectivity in analytical chemistry: two interpretations for univariate methods.

    Science.gov (United States)

    Dorkó, Zsanett; Verbić, Tatjana; Horvai, George

    2015-01-01

    Selectivity is extremely important in analytical chemistry but its definition is elusive despite continued efforts by professional organizations and individual scientists. This paper shows that the existing selectivity concepts for univariate analytical methods broadly fall in two classes: selectivity concepts based on measurement error and concepts based on response surfaces (the response surface being the 3D plot of the univariate signal as a function of analyte and interferent concentration, respectively). The strengths and weaknesses of the different definitions are analyzed and contradictions between them unveiled. The error based selectivity is very general and very safe but its application to a range of samples (as opposed to a single sample) requires the knowledge of some constraint about the possible sample compositions. The selectivity concepts based on the response surface are easily applied to linear response surfaces but may lead to difficulties and counterintuitive results when applied to nonlinear response surfaces. A particular advantage of this class of selectivity is that with linear response surfaces it can provide a concentration independent measure of selectivity. In contrast, the error based selectivity concept allows only yes/no type decision about selectivity.

  16. A Selection of Recent Advances in C1 Chemistry.

    Science.gov (United States)

    Mesters, Carl

    2016-06-01

    This review presents a selection of recent publications related to the chemistry and catalysis of C1 molecules, including methane, methanol, carbon monoxide, and carbon dioxide. These molecules play an important role in the current supply of energy and chemicals and will likely become even more relevant because of the need to decarbonize fuels (shift from coal to natural gas) in line with CO2 capture and use to mitigate global warming, as well as a gradual shift on the supply side from crude oil to natural gas. This review includes both recent industrial developments, such as the huge increase in methanol-to-olefins-capacity build in China and the demonstration of oxidative coupling of methane, and scientific developments in these chemistries facilitated by improved capabilities in, for example, analytical tools and computational modeling. PMID:27276549

  17. Recent advances in heterogeneous selective oxidation catalysis for sustainable chemistry.

    Science.gov (United States)

    Guo, Zhen; Liu, Bin; Zhang, Qinghong; Deng, Weiping; Wang, Ye; Yang, Yanhui

    2014-05-21

    Oxidation catalysis not only plays a crucial role in the current chemical industry for the production of key intermediates such as alcohols, epoxides, aldehydes, ketones and organic acids, but also will contribute to the establishment of novel green and sustainable chemical processes. This review is devoted to dealing with selective oxidation reactions, which are important from the viewpoint of green and sustainable chemistry and still remain challenging. Actually, some well-known highly challenging chemical reactions involve selective oxidation reactions, such as the selective oxidation of methane by oxygen. On the other hand some important oxidation reactions, such as the aerobic oxidation of alcohols in the liquid phase and the preferential oxidation of carbon monoxide in hydrogen, have attracted much attention in recent years because of their high significance in green or energy chemistry. This article summarizes recent advances in the development of new catalytic materials or novel catalytic systems for these challenging oxidation reactions. A deep scientific understanding of the mechanisms, active species and active structures for these systems are also discussed. Furthermore, connections among these distinct catalytic oxidation systems are highlighted, to gain insight for the breakthrough in rational design of efficient catalytic systems for challenging oxidation reactions.

  18. A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms

    Directory of Open Access Journals (Sweden)

    G. Sarwar

    2013-10-01

    Full Text Available We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2 into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyacetyl nitrate by 40%, and organic nitrate by 41%. RACM2 enhances ozone compared to CB05TU at all ambient levels. Although it exhibited greater overestimates at lower observed concentrations, it displayed an improved performance at higher observed concentrations. The RACM2 ozone predictions are also supported by increased ozone production efficiency that agrees better with observations. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean sulfate by 10%, nitrate by 6%, ammonium by 10%, anthropogenic secondary organic aerosols by 42%, biogenic secondary organic aerosols by 5%, and in-cloud secondary organic aerosols by 7%. Increased inorganic and organic aerosols with RACM2 agree better with observed data. Any air pollution control strategies developed using the two mechanisms do not differ appreciably.

  19. A comparison of atmospheric composition using the Carbon Bond and Regional Atmospheric Chemistry Mechanisms

    Directory of Open Access Journals (Sweden)

    G. Sarwar

    2013-03-01

    Full Text Available We incorporate the recently developed Regional Atmospheric Chemistry Mechanism (version 2, RACM2 into the Community Multiscale Air Quality modeling system for comparison with the existing 2005 Carbon Bond mechanism with updated toluene chemistry (CB05TU. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean hydroxyl radical concentrations by 46% and nitric acid by 26%. However, it reduces hydrogen peroxide by 2%, peroxyacetic acid by 94%, methyl hydrogen peroxide by 19%, peroxyacetyl nitrate by 40%, and organic nitrate by 41%. RACM2 predictions generally agree better with the observed data than the CB05TU predictions. RACM2 enhances ozone for all ambient levels leading to higher bias at low (70 ppbv concentrations. The RACM2 ozone predictions are also supported by increased ozone production efficiency that agrees better with observations. Compared to CB05TU, RACM2 enhances the domain-wide monthly mean sulfate by 10%, nitrate by 6%, ammonium by 10%, anthropogenic secondary organic aerosols by 42%, biogenic secondary organic aerosols by 5%, and in-cloud secondary organic aerosols by 7%. Increased inorganic and organic aerosols with RACM2 agree better with observed data. While RACM2 enhances ozone and secondary aerosols by relatively large margins, control strategies developed for ozone or fine particles using the two mechanisms do not differ appreciably.

  20. Organic chemistry. Functionalization of C(sp3)-H bonds using a transient directing group.

    Science.gov (United States)

    Zhang, Fang-Lin; Hong, Kai; Li, Tuan-Jie; Park, Hojoon; Yu, Jin-Quan

    2016-01-15

    Proximity-driven metalation has been extensively exploited to achieve reactivity and selectivity in carbon-hydrogen (C-H) bond activation. Despite the substantial improvement in developing more efficient and practical directing groups, their stoichiometric installation and removal limit efficiency and, often, applicability as well. Here we report the development of an amino acid reagent that reversibly reacts with aldehydes and ketones in situ via imine formation to serve as a transient directing group for activation of inert C-H bonds. Arylation of a wide range of aldehydes and ketones at the β or γ positions proceeds in the presence of a palladium catalyst and a catalytic amount of amino acid. The feasibility of achieving enantioselective C-H activation reactions using a chiral amino acid as the transient directing group is also demonstrated.

  1. Bias-controlled selective excitation of vibrational modes in molecular junctions: a route towards mode-selective chemistry.

    Science.gov (United States)

    Volkovich, Roie; Härtle, Rainer; Thoss, Michael; Peskin, Uri

    2011-08-28

    We show that individual vibrational modes in single-molecule junctions with asymmetric molecule-lead coupling can be selectively excited by applying an external bias voltage. Thereby, a non-statistical distribution of vibrational energy can be generated, that is, a mode with a higher frequency can be stronger excited than a mode with a lower frequency. This is of particular interest in the context of mode-selective chemistry, where one aims to break specific (not necessarily the weakest) chemical bond in a molecule. Such mode-selective vibrational excitation is demonstrated for two generic model systems representing asymmetric molecular junctions and/or scanning tunneling microscopy experiments. To this end, we employ two complementary theoretical approaches, a nonequilibrium Green's function approach and a master equation approach. The comparison of both methods reveals good agreement in describing resonant electron transport through a single-molecule contact, where differences between the approaches highlight the role of non-resonant transport processes, in particular co-tunneling and off-resonant electron-hole pair creation processes.

  2. Surface Chemistry at Size-Selected Nano-Aerosol Particles

    Science.gov (United States)

    Roberts, Jeffrey

    2005-03-01

    A method has been developed to conduct surface chemistry and extract surface kinetic rates from size-selected aerosol nanoparticles. The measurements encompass broad ranges of particle size, phase, and composition. Results will be presented on the uptake of water by aerosolized soot nanoparticles of radius between 10 and 40 nm. Water uptake was monitored by tandem differential mobility analysis (T-DMA), which is capable of measuring changes in particle diameter as little as 0.2 nm. Soot particles were produced in an ethene diffusion flame and extracted into an atmospheric pressure aerosol flow tube reactor. The particles were subjected to various thermal and oxidative treatments, and the effects of these treatments on the ability of soot to adsorb monolayer quantities of water was determined. The results are important because soot nucleates atmospheric cloud particles. More generally, the results represent one of the first kinetic and mechanistic studies of gas-phase nanoparticle reactivity. Co-author: Henry Ajo, University of Minnesota

  3. Application of the Covalent Bond Classification Method for the Teaching of Inorganic Chemistry

    Science.gov (United States)

    Green, Malcolm L. H.; Parkin, Gerard

    2014-01-01

    The Covalent Bond Classification (CBC) method provides a means to classify covalent molecules according to the number and types of bonds that surround an atom of interest. This approach is based on an elementary molecular orbital analysis of the bonding involving the central atom (M), with the various interactions being classified according to the…

  4. The chemistry of simple alkene molecules on Si(100)c(4 × 2): The mechanism of cycloaddition and their selectivities

    Science.gov (United States)

    Akagi, Kazuto; Yoshinobu, Jun

    2016-10-01

    The chemistry of simple alkene molecules on the Si(100) surface is reviewed with the newly-produced visual presentation by theoretical calculations. The early pioneering studies by the Kyoto Group and Pittsburgh group reported the di-σ bond formation and the precursor-mediated chemisorption for acetylene and ethylene on Si(100), respectively. Thereafter, these studies have been stimulating various studies of organic molecules on Si surfaces. Our recent studies have observed the precursor states for alkene chemisorption and elucidated the microscopic mechanisms of the di-σ bond formation (cycloaddition) with the help of theoretical calculations; the site-, stereo- and regio-selective chemisorption of simple alkene molecules on Si(100)c(4 × 2) has been established.

  5. Rocky Mountain snowpack chemistry at selected sites for 2001

    Science.gov (United States)

    Ingersoll, George P.; Mast, M. Alisa; Clow, David W.; Nanus, Leora; Campbell, Donald H.; Handran, Heather

    2003-01-01

    Because regional-scale atmospheric deposition data in the Rocky Mountains are sparse, a program was designed by the U.S. Geological Survey, in cooperation with the National Park Service, U.S. Department of Agriculture Forest Service, and other agencies, to more thoroughly determine the chemical composition of precipitation and to identify sources of atmospherically deposited contaminants in a network of high-elevation sites. Samples of seasonal snowpacks at 57 geographically distributed sites, in a regional network from New Mexico to Montana, were collected and analyzed for major ions (including ammonium, nitrate, and sulfate), alkalinity, and dissolved organic carbon during 2001. Sites selected in this report have been sampled annually since 1993, enabling identification of increases or decreases in chemical concentrations from year to year. Spatial patterns in snowpack-chemical data for concentrations of ammonium, nitrate, and sulfate indicate that concentrations of these acid precursors in less developed areas of the region are lower than concentrations in the heavily developed areas. Results for the 2001 snowpack-chemistry analyses, however, indicate increases in concentrations of ammonium and nitrate in particular at sites where past concentrations typically were lower. Since 1993, concentrations of nitrate and sulfate were highest from snowpack samples in northern Colorado that were collected from sites adjacent to the Denver metropolitan area to the east and the coal-fired powerplants to the west. In 2001, relatively high concentrations of nitrate (12.3 to 23.0 microequivalents per liter (?eq/L) and sulfate (7.7 to 12.5 ?eq/L) were detected in Montana and Wyoming. Ammonium concentrations were highest in north-central Colorado (14.5 to 16.9 ?eq/L) and southwestern Montana (12.8 to 14.2 ?eq/L).

  6. Mode specificity in bond selective reactions F + HOD → HF + OD and DF + OH

    Energy Technology Data Exchange (ETDEWEB)

    Song, Hongwei; Guo, Hua, E-mail: hguo@unm.edu [Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

    2015-05-07

    The influence of vibrational excitations in the partially deuterated water (HOD) reactant on its bond selective reactions with F is investigated using a full-dimensional quantum wave packet method on an accurate global potential energy surface. Despite the decidedly early barrier of the F + H{sub 2}O reaction, reactant vibrational excitation in each local stretching mode of HOD is found to significantly enhance the reaction which breaks the excited bond. In the mean time, excitation of the HOD bending mode also enhances the reaction, but with much lower efficacy and weaker bond selectivity. Except for low collision energies, all vibrational modes are more effective in promoting the bond selective reactions than the translational energy. These results are compared with the predictions of the recently proposed sudden vector projection model.

  7. Understanding The Role of Mate Selection Processes in Couples' Pair-Bonding Behavior.

    Science.gov (United States)

    Horwitz, Briana N; Reynolds, Chandra A; Walum, Hasse; Ganiban, Jody; Spotts, Erica L; Reiss, David; Lichtenstein, Paul; Neiderhiser, Jenae M

    2016-01-01

    Couples are similar in their pair-bonding behavior, yet the reasons for this similarity are often unclear. A common explanation is phenotypic assortment, whereby individuals select partners with similar heritable characteristics. Alternatively, social homogamy, whereby individuals passively select partners with similar characteristic due to shared social backgrounds, is rarely considered. We examined whether phenotypic assortment and/or social homogamy can contribute to mate similarity using a twin-partner design. The sample came from the Twin and Offspring Study in Sweden, which included 876 male and female monozygotic and same-sex dizygotic twins plus their married or cohabitating partners. Results showed that variance in pair-bonding behavior was attributable to genetic and nonshared environmental factors. Furthermore, phenotypic assortment accounted for couple similarity in pair-bonding behavior. This suggests that individuals' genetically based characteristics are involved in their selection of mates with similar pair-bonding behavior.

  8. The Influence of Computer-Assisted Instruction on Students' Conceptual Understanding of Chemical Bonding and Attitude toward Chemistry: A Case for Turkey

    Science.gov (United States)

    Ozmen, Haluk

    2008-01-01

    In this study, the effect of computer-assisted instruction on conceptual understanding of chemical bonding and attitude toward chemistry was investigated. The study employed a quasi-experimental design involving 11 grade students; 25 in an experimental and 25 in a control group. The Chemical Bonding Achievement Test (CBAT) consisting of 15…

  9. Solutions to selected exercise problems in quantum chemistry and spectroscopy

    DEFF Research Database (Denmark)

    Spanget-Larsen, Jens

    2016-01-01

    Suggested solutions to a number of problems from the collection "Exercise Problems in Quantum Chemistry and Spectroscopy", previously published on ResearchGate (DOI: 10.13140/RG.2.1.4024.8162).......Suggested solutions to a number of problems from the collection "Exercise Problems in Quantum Chemistry and Spectroscopy", previously published on ResearchGate (DOI: 10.13140/RG.2.1.4024.8162)....

  10. Demystifying Introductory Chemistry. Part 2: Bonding and Molecular Geometry Without Orbitals--the Electron Domain Model.

    Science.gov (United States)

    Gillespie, Ronald J.; And Others

    1996-01-01

    Presents an alternative approach to bonding and geometry--the electron domain model--which avoids some of the problems with the conventional approach. Discusses difficulties with the orbital model at the introductory level, electron spin and the Pauli exclusion principle, electron pair domains, nonequivalent domains, multiple bonds, and origins…

  11. Bonds Between Metal Atoms: A New Mode of Transition Metal Chemistry.

    Science.gov (United States)

    Cotton, F. Albert; Chisholm, Malcolm H.

    1982-01-01

    Discusses polynuclear metal clusters (containing two or more metal atoms bonded to one another as well as to nonmetallic elements), including their formation and applications. Studies of bonds between metal atoms reveal superconductors, organic-reaction catalysts, and photosensitive complexes that may play a role in solar energy. (JN)

  12. Exploring the uranyl organometallic chemistry: from single to double uranium carbon bonds

    International Nuclear Information System (INIS)

    Uranyl organometallic complexes featuring uranium(VI) carbon single and double bonds have been obtained from uranyl UO2X2 precursors by avoiding reduction of the metal center. X-ray diffraction and density functional theory analyses of these complexes showed that the UC and UdC bonds are polarized toward the nucleophilic carbon. (authors)

  13. Investigating Hydrogen Bonding in Phenol Using Infrared Spectroscopy and Computational Chemistry

    Science.gov (United States)

    Fedor, Anna M.; Toda, Megan J.

    2014-01-01

    The hydrogen bonding of phenol can be used as an introductory model for biological systems because of its structural similarities to tyrosine, a para-substituted phenol that is an amino acid essential to the synthesis of proteins. Phenol is able to form hydrogen bonds readily in solution, which makes it a suitable model for biological…

  14. Selective Nitrate Recognition by a Halogen-Bonding Four-Station [3]Rotaxane Molecular Shuttle.

    Science.gov (United States)

    Barendt, Timothy A; Docker, Andrew; Marques, Igor; Félix, Vítor; Beer, Paul D

    2016-09-01

    The synthesis of the first halogen bonding [3]rotaxane host system containing a bis-iodo triazolium-bis-naphthalene diimide four station axle component is reported. Proton NMR anion binding titration experiments revealed the halogen bonding rotaxane is selective for nitrate over the more basic acetate, hydrogen carbonate and dihydrogen phosphate oxoanions and chloride, and exhibits enhanced recognition of anions relative to a hydrogen bonding analogue. This elaborate interlocked anion receptor functions via a novel dynamic pincer mechanism where upon nitrate anion binding, both macrocycles shuttle from the naphthalene diimide stations at the periphery of the axle to the central halogen bonding iodo-triazolium station anion recognition sites to form a unique 1:1 stoichiometric nitrate anion-rotaxane sandwich complex. Molecular dynamics simulations carried out on the nitrate and chloride halogen bonding [3]rotaxane complexes corroborate the (1) H NMR anion binding results. PMID:27436297

  15. Selectivity of peptide bond dissociation on excitation of a core electron: Effects of a phenyl group

    Science.gov (United States)

    Tsai, Cheng-Cheng; Chen, Jien-Lian; Hu, Wei-Ping; Lin, Yi-Shiue; Lin, Huei-Ru; Lee, Tsai-Yun; Lee, Yuan T.; Ni, Chi-Kung; Liu, Chen-Lin

    2016-09-01

    The selective dissociation of a peptide bond upon excitation of a core electron in acetanilide and N-benzylacetamide was investigated. The total-ion-yield near-edge X-ray absorption fine structure spectra were recorded and compared with the predictions from time-dependent density functional theory. The branching ratios for the dissociation of a peptide bond are observed as 16-34% which is quite significant. This study explores the core-excitation, the X-ray photodissociation pathways, and the theoretical explanation of the NEXAFS spectra of organic molecules containing both a peptide bond and a phenyl group.

  16. Metabolic Engineering to Develop a Pathway for the Selective Cleavage of Carbon-Nitrogen Bonds

    Energy Technology Data Exchange (ETDEWEB)

    John J. Kilbane II

    2005-10-01

    The objective of the project is to develop a biochemical pathway for the selective cleavage of C-N bonds in molecules found in petroleum. Specifically a novel biochemical pathway will be developed for the selective cleavage of C-N bonds in carbazole. The cleavage of the first C-N bond in carbazole is accomplished by the enzyme carbazole dioxygenase, that catalyzes the conversion of carbazole to 2-aminobiphenyl-2,3-diol. The genes encoding carbazole dioxygenase were cloned from Sphingomonas sp. GTIN11 and from Pseudomonas resinovorans CA10. The selective cleavage of the second C-N bond has been challenging, and efforts to overcome that challenge have been the focus of recent research in this project. Enrichment culture experiments succeeded in isolating bacterial cultures that can metabolize 2-aminobiphenyl, but no enzyme capable of selectively cleaving the C-N bond in 2-aminobiphenyl has been identified. Aniline is very similar to the structure of 2-aminobiphenyl and aniline dioxygenase catalyzes the conversion of aniline to catechol and ammonia. For the remainder of the project the emphasis of research will be to simultaneously express the genes for carbazole dioxygenase and for aniline dioxygenase in the same bacterial host and then to select for derivative cultures capable of using carbazole as the sole source of nitrogen.

  17. New Mechanistic Insights on the Selectivity of Transition-Metal-Catalyzed Organic Reactions: The Role of Computational Chemistry.

    Science.gov (United States)

    Zhang, Xinhao; Chung, Lung Wa; Wu, Yun-Dong

    2016-06-21

    With new advances in theoretical methods and increased computational power, applications of computational chemistry are becoming practical and routine in many fields of chemistry. In organic chemistry, computational chemistry plays an indispensable role in elucidating reaction mechanisms and the origins of various selectivities, such as chemo-, regio-, and stereoselectivities. Consequently, mechanistic understanding improves synthesis and assists in the rational design of new catalysts. In this Account, we present some of our recent works to illustrate how computational chemistry provides new mechanistic insights for improvement of the selectivities of several organic reactions. These examples include not only explanations for the existing experimental observations, but also predictions which were subsequently verified experimentally. This Account consists of three sections discuss three different kinds of selectivities. The first section discusses the regio- and stereoselectivities of hydrosilylations of alkynes, mainly catalyzed by [Cp*Ru(MeCN)3](+) or [CpRu(MeCN)3](+). Calculations suggest a new mechanism that involves a key ruthenacyclopropene intermediate. This mechanism not only explains the unusual Markovnikov regio-selectivity and anti-addition stereoselectivity observed by Trost and co-workers, but also motivated further experimental investigations. New intriguing experimental observations and further theoretical studies led to an extension of the reaction mechanism. The second section includes three cases of meta-selective C-H activation of aryl compounds. In the case of Cu-catalyzed selective meta-C-H activation of aniline, a new mechanism that involves a Cu(III)-Ar-mediated Heck-like transition state, in which the Ar group acts as an electrophile, was proposed. This mechanism predicted a higher reactivity for more electron-deficient Ar groups, which was supported by experiments. For two template-mediated, meta-selective C-H bond activations catalyzed by

  18. New Mechanistic Insights on the Selectivity of Transition-Metal-Catalyzed Organic Reactions: The Role of Computational Chemistry.

    Science.gov (United States)

    Zhang, Xinhao; Chung, Lung Wa; Wu, Yun-Dong

    2016-06-21

    With new advances in theoretical methods and increased computational power, applications of computational chemistry are becoming practical and routine in many fields of chemistry. In organic chemistry, computational chemistry plays an indispensable role in elucidating reaction mechanisms and the origins of various selectivities, such as chemo-, regio-, and stereoselectivities. Consequently, mechanistic understanding improves synthesis and assists in the rational design of new catalysts. In this Account, we present some of our recent works to illustrate how computational chemistry provides new mechanistic insights for improvement of the selectivities of several organic reactions. These examples include not only explanations for the existing experimental observations, but also predictions which were subsequently verified experimentally. This Account consists of three sections discuss three different kinds of selectivities. The first section discusses the regio- and stereoselectivities of hydrosilylations of alkynes, mainly catalyzed by [Cp*Ru(MeCN)3](+) or [CpRu(MeCN)3](+). Calculations suggest a new mechanism that involves a key ruthenacyclopropene intermediate. This mechanism not only explains the unusual Markovnikov regio-selectivity and anti-addition stereoselectivity observed by Trost and co-workers, but also motivated further experimental investigations. New intriguing experimental observations and further theoretical studies led to an extension of the reaction mechanism. The second section includes three cases of meta-selective C-H activation of aryl compounds. In the case of Cu-catalyzed selective meta-C-H activation of aniline, a new mechanism that involves a Cu(III)-Ar-mediated Heck-like transition state, in which the Ar group acts as an electrophile, was proposed. This mechanism predicted a higher reactivity for more electron-deficient Ar groups, which was supported by experiments. For two template-mediated, meta-selective C-H bond activations catalyzed by

  19. Consistent descriptions of metal–ligand bonds and spin-crossover in inorganic chemistry

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2013-01-01

    Density functional theory (DFT) is today the unchallenged tool for routinely obtaining molecular information on chemical stability, reactivity, and electronic structure across the Periodic Table. The chemical bond is the fundamental unit of molecular structure and reactivity, and thus, large...

  20. Variable selectivity of the Hitachi chemistry analyzer chloride ion-selective electrode toward interfering ions.

    Science.gov (United States)

    Wang, T; Diamandis, E P; Lane, A; Baines, A D

    1994-02-01

    Chloride measurements by ion-selective electrodes are vulnerable to interference by anions such as iodide, thiocyanate, nitrate, and bromide. We have found that the degree of interference of these anions on the Hitachi chemistry analyzer chloride electrode varies from electrode to electrode and this variation can even occur within the same lot of membrane. This variation is not dependent upon the length of time the cartridge has been in the analyzer because no correlation existed between the usage time and the electrode response to interfering ions. Neither is this variation due to the deterioration of the electrode because all electrodes tested had calibration slopes within the manufacturer's specification. Our study, however, showed that even after repeated exposure to a plasma sample containing 2 mM thiocyanate, the chloride electrode was still able to accurately measure the chloride in plasma without thiocyanate, thus confirming that a carryover effect does not exist from a previous thiocyanate-containing sample.

  1. Extending Stannyl Anion Chemistry to the Actinides: Synthesis and Characterization of a Uranium-Tin Bond.

    Science.gov (United States)

    Winston, Matthew S; Batista, Enrique R; Yang, Ping; Tondreau, Aaron M; Boncella, James M

    2016-06-01

    We have synthesized a rare example of a uranium(IV) stannyl (κ(4)-N(CH2CH2NSi((i)Pr)3)3U(SnMe3), 1) via transmetalation with LiSnMe3. This complex has been characterized crystallographically and shown to have a U-Sn bond length of 3.3130(3) Å, substantially longer than the only other crystallographically observed U-Sn bond (3.166 Å). Computational studies suggest that the U-Sn bond in 1 is highly polarized, with significant charge transfer to the stannylate ligand. We briefly discuss plausible mechanistic scenarios for the formation of 1, which may be relevant to other transmetalation processes involving heavy main group atoms. Furthermore, we demonstrate the reducing ability of [SnMe3](-) in the absence of strongly donating ligands on U(IV). PMID:27219499

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-11-27

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

  3. Localized removal of the Au-Si eutectic bonding layer for the selective release of microstructures

    Science.gov (United States)

    Gradin, Henrik; Braun, Stefan; Stemme, Göran; van der Wijngaart, Wouter

    2009-10-01

    This paper presents and investigates a novel technique for the footprint and thickness-independent selective release of Au-Si eutectically bonded microstructures through the localized removal of their eutectic bond interface. The technique is based on the electrochemical removal of the gold in the eutectic layer and the selectivity is provided by patterning the eutectic layer and by proper electrical connection or isolation of the areas to be etched or removed, respectively. The gold removal results in a porous silicon layer, acting similar to standard etch holes in a subsequent sacrificial release etching. The paper presents the principle and the design requirements of the technique. First test devices were fabricated and the method successfully demonstrated. Furthermore, the paper investigates the release mechanism and the effects of different gold layouts on both the eutectic bonding and the release procedure.

  4. Localized removal of the Au–Si eutectic bonding layer for the selective release of microstructures

    International Nuclear Information System (INIS)

    This paper presents and investigates a novel technique for the footprint and thickness-independent selective release of Au–Si eutectically bonded microstructures through the localized removal of their eutectic bond interface. The technique is based on the electrochemical removal of the gold in the eutectic layer and the selectivity is provided by patterning the eutectic layer and by proper electrical connection or isolation of the areas to be etched or removed, respectively. The gold removal results in a porous silicon layer, acting similar to standard etch holes in a subsequent sacrificial release etching. The paper presents the principle and the design requirements of the technique. First test devices were fabricated and the method successfully demonstrated. Furthermore, the paper investigates the release mechanism and the effects of different gold layouts on both the eutectic bonding and the release procedure

  5. NMR Determination of Hydrogen Bond Thermodynamics in a Simple Diamide: A Physical Chemistry Experiment

    Science.gov (United States)

    Morton, Janine G.; Joe, Candice L.; Stolla, Massiel C.; Koshland, Sophia R.; Londergan, Casey H.; Schofield, Mark H.

    2015-01-01

    Variable temperature NMR spectroscopy is used to determine the ?H° and ?S° of hydrogen bond formation in a simple diamide. In this two- or three-day experiment, students synthesize N,N'-dimethylmalonamide, dimethylsuccinamide, dimethylglutaramide, or dimethyladipamide from methylamine and the corresponding diester (typically in 50% recrystallized…

  6. Selective Breaking of Hydrogen Bonds of Layered Carbon Nitride for Visible Light Photocatalysis.

    Science.gov (United States)

    Kang, Yuyang; Yang, Yongqiang; Yin, Li-Chang; Kang, Xiangdong; Wang, Lianzhou; Liu, Gang; Cheng, Hui-Ming

    2016-08-01

    Selective breaking of the hydrogen bonds of graphitic carbon nitride can introduce favorable features, including increased band tails close to the band edges and the creation of abundant pores. These features can simultaneously improve the three basic processes of photocatalysis. As a consequence, the photocatalytic hydrogen-generation activity of carbon nitride under visible light is drastically increased by tens of times.

  7. The C–F bond as a conformational tool in organic and biological chemistry

    Directory of Open Access Journals (Sweden)

    Luke Hunter

    2010-04-01

    Full Text Available Organofluorine compounds are widely used in many different applications, ranging from pharmaceuticals and agrochemicals to advanced materials and polymers. It has been recognised for many years that fluorine substitution can confer useful molecular properties such as enhanced stability and hydrophobicity. Another impact of fluorine substitution is to influence the conformations of organic molecules. The stereoselective introduction of fluorine atoms can therefore be exploited as a conformational tool for the synthesis of shape-controlled functional molecules. This review will begin by describing some general aspects of the C–F bond and the various conformational effects associated with C–F bonds (i.e. dipole–dipole interactions, charge–dipole interactions and hyperconjugation. Examples of functional molecules that exploit these conformational effects will then be presented, drawing from a diverse range of molecules including pharmaceuticals, organocatalysts, liquid crystals and peptides.

  8. The C–F bond as a conformational tool in organic and biological chemistry

    Science.gov (United States)

    2010-01-01

    Summary Organofluorine compounds are widely used in many different applications, ranging from pharmaceuticals and agrochemicals to advanced materials and polymers. It has been recognised for many years that fluorine substitution can confer useful molecular properties such as enhanced stability and hydrophobicity. Another impact of fluorine substitution is to influence the conformations of organic molecules. The stereoselective introduction of fluorine atoms can therefore be exploited as a conformational tool for the synthesis of shape-controlled functional molecules. This review will begin by describing some general aspects of the C–F bond and the various conformational effects associated with C–F bonds (i.e. dipole–dipole interactions, charge–dipole interactions and hyperconjugation). Examples of functional molecules that exploit these conformational effects will then be presented, drawing from a diverse range of molecules including pharmaceuticals, organocatalysts, liquid crystals and peptides. PMID:20502650

  9. Aluminum germanides of the divalent lanthanoides Eu and Yb. Synthesis, structural chemistry and chemical bonding

    International Nuclear Information System (INIS)

    In the course of attempts to substitute Ca by Yb and Sr by Eu in known alkaline earth Al-germanides, the four new ternary compounds Eu3Al1.8Ge2.2, Eu3Al2Ge4, Yb2AlGe3, and Yb17Al8Ge19 have been synthesized from mixtures of the elements and their crystal structures determined by means of single-crystal X-ray data. The two europium compounds Eu3Al1.8Ge2.2 (Ta3B4 structure type, orthorhombic, space group Immm, a = 417.68(3), b = 470.70(3), c = 1897.2(2) pm, Z = 2, R1 = 0.0439) and Eu3Al2Ge4 (Sr3Al2Ge4 structure type, monoclinic, space group C2/m, a = 1235.9(6), b = 416.8(2), c = 878.4(4) pm, β = 110.615(13) , Z = 2, R1 = 0.0978) are isotypic with the corresponding strontium phases. After ionic decomposition, the layers [Al-2Ge-4]6- in Eu3Al2Ge4 with four-bonded Al and three-bonded Ge atoms can be interpreted as electron-precise Zintl anions. In contrast, the planar ribbons 1∞[Al2/2Ge2Al2/2] of condensed six-membered rings in Eu3Al1.8Ge2.2 exhibit considerably shorter Al-Ge bonds and an Al-Al bond length of only 251 pm. Yb2AlGe3 (orthorhombic, space group Pnma, a = 682.20(10), b = 417.87(9), c = 1813.9(3) pm, Z = 4, R1 = 0.0415) crystallizes with the Y2AlGe3 structure type. Folded [Al2Ge2] ladders, also found in Eu3Al2Ge4 and the known compound Yb7Al5Ge8, are connected by planar cis/trans chains of Ge atoms. The total density of states calculated within the FP-LAPW DFT band structure approach shows a distinct minimum at the Fermi level for the electron precise Zintl compound Eu3Al2Ge4, whereas π-bonding contributions are evident from the band structures of Eu3Al2Ge2 and Yb2AlGe3. In full accordance, the tDOS of both compounds exhibits no minimum at EF, small phase widths are possible for Eu3Al2Ge2 and related alkaline earth compounds, and Yb2AlGe3 is isotypic with several other more electron-rich LnIII compounds. The complicated structure of the new compound Yb17Al8Ge19 (tetragonal, space group P4/nmm, a = 1542.50(2), c = 788.285(8) pm, Z = 2, R1 = 0.0282) contains

  10. METABOLIC ENGINEERING TO DEVELOP A PATHWAY FOR THE SELECTIVE CLEAVAGE OF CARBON-NITROGEN BONDS

    Energy Technology Data Exchange (ETDEWEB)

    John J. Kilbane II

    2004-10-01

    The objective of the project is to develop biochemical pathways for the selective cleavage of C-N bonds in molecules found in petroleum. The initial phase of the project was focused on the isolation or development of an enzyme capable of cleaving the C-N bond in aromatic amides, specifically 2-aminobiphenyl. The objective of the second phase of the research will be to construct a biochemical pathway for the selective removal of nitrogen from carbazole by combining the carA genes from Sphingomonas sp. GTIN11 with the gene(s) encoding an appropriate deaminase. The objective of the final phase of the project will be to develop derivative C-N bond cleaving enzymes that have broader substrate ranges and to demonstrate the use of such strains to selectively remove nitrogen from petroleum. During the first year of the project (October, 2002-September, 2003) enrichment culture experiments resulted in the isolation of microbial cultures that utilize aromatic amides as sole nitrogen sources, several amidase genes were cloned and were included in directed evolution experiments to obtain derivatives that can cleave C-N bonds in aromatic amides, and the carA genes from Sphingomonas sp. GTIN11, and Pseudomonas resinovorans CA10 were cloned in vectors capable of replicating in Escherichia coli. During the second year of the project (October, 2003-September, 2004) enrichment culture experiments succeeded in isolating a mixed bacterial culture that can utilize 2-aminobiphenyl as a sole nitrogen source, directed evolution experiments were focused on the aniline dioxygenase enzyme that is capable of deaminating aniline, and expression vectors were constructed to enable the expression of genes encoding C-N bond cleaving enzymes in Rhodococcus hosts. The construction of a new metabolic pathway to selectively remove nitrogen from carbazole and other molecules typically found in petroleum should lead to the development of a process to improve oil refinery efficiency by reducing the

  11. Strong Coupling between Nanofluidic Transport and Interfacial Chemistry: How Defect Reactivity Controls Liquid-Solid Friction through Hydrogen Bonding.

    Science.gov (United States)

    Joly, Laurent; Tocci, Gabriele; Merabia, Samy; Michaelides, Angelos

    2016-04-01

    Defects are inevitably present in nanofluidic systems, yet the role they play in nanofluidic transport remains poorly understood. Here, we report ab initio molecular dynamics (AIMD) simulations of the friction of liquid water on defective graphene and boron nitride sheets. We show that water dissociates at certain defects and that these "reactive" defects lead to much larger friction than the "nonreactive" defects at which water molecules remain intact. Furthermore, we find that friction is extremely sensitive to the chemical structure of reactive defects and to the number of hydrogen bonds they can partake in with the liquid. Finally, we discuss how the insight obtained from AIMD can be used to quantify the influence of defects on friction in nanofluidic devices for water treatment and sustainable energy harvesting. Overall, we provide new insight into the role of interfacial chemistry on nanofluidic transport in real, defective systems. PMID:27012818

  12. Merging allylic carbon-hydrogen and selective carbon-carbon bond activation

    Science.gov (United States)

    Masarwa, Ahmad; Didier, Dorian; Zabrodski, Tamar; Schinkel, Marvin; Ackermann, Lutz; Marek, Ilan

    2014-01-01

    Since the nineteenth century, many synthetic organic chemists have focused on developing new strategies to regio-, diastereo- and enantioselectively build carbon-carbon and carbon-heteroatom bonds in a predictable and efficient manner. Ideal syntheses should use the least number of synthetic steps, with few or no functional group transformations and by-products, and maximum atom efficiency. One potentially attractive method for the synthesis of molecular skeletons that are difficult to prepare would be through the selective activation of C-H and C-C bonds, instead of the conventional construction of new C-C bonds. Here we present an approach that exploits the multifold reactivity of easily accessible substrates with a single organometallic species to furnish complex molecular scaffolds through the merging of otherwise difficult transformations: allylic C-H and selective C-C bond activations. The resulting bifunctional nucleophilic species, all of which have an all-carbon quaternary stereogenic centre, can then be selectively derivatized by the addition of two different electrophiles to obtain more complex molecular architecture from these easily available starting materials.

  13. METABOLIC ENGINEERING TO DEVELOP A PATHWAY FOR THE SELECTIVE CLEAVAGE OF CARBON-NITROGEN BONDS

    Energy Technology Data Exchange (ETDEWEB)

    John J. Kilbane III

    2003-12-01

    The objective of the project is to develop biochemical pathways for the selective cleavage of C-N bonds in molecules found in petroleum. The initial phase of the project will focus on the isolation or development of an enzyme capable of cleaving the C-N bond in aromatic amides, specifically 2-aminobiphenyl. The objective of the second phase of the research will be to construct a biochemical pathway for the selective removal of nitrogen from carbazole by combining the carA genes from Sphingomonas sp. GTIN11 with the gene(s) encoding an appropriate amidase. The objective of the final phase of the project will be to develop derivative CN bond cleaving enzymes that have broader substrate ranges and to demonstrate the use of such strains to selectively remove nitrogen from petroleum. The project is on schedule and no major difficulties have been encountered. During the first year of the project (October, 2002-September, 2003) enrichment culture experiments have resulted in the isolation of promising cultures that may be capable of cleaving C-N bonds in aromatic amides, several amidase genes have been cloned and are currently undergoing directed evolution to obtain derivatives that can cleave C-N bonds in aromatic amides, and the carA genes from Sphingomonas sp. GTIN11, and Pseudomonas resinovorans CA10 were cloned in vectors capable of replicating in Escherichia coli. Future research will address expression of these genes in Rhodococcus erythropolis. Enrichment culture experiments and directed evolution experiments continue to be a main focus of research activity and further work is required to obtain an appropriate amidase that will selectively cleave C-N bonds in aromatic substrates. Once an appropriate amidase gene is obtained it must be combined with genes encoding an enzyme capable of converting carbazole to 2'aminobiphenyl-2,3-diol: specifically carA genes. The carA genes from two sources have been cloned and are ready for construction of C-N bond cleavage

  14. Implementation and Evaluation of Web-Based Learning Activities on Bonding and the Structure of Matter for 10-th Grade Chemistry

    Science.gov (United States)

    Frailich, Marcel

    This study deals with the development, implementation, and evaluation of web-based activities associated with the topic of chemical bonding , as taught in 10th grade chemistry. A website was developed entitled: "Chemistry and the Chemical Industry in the Service of Mankind", its URL is: http://stwww.weizmann.ac.il/g-chem/learnchem (Kesner, Frailich, & Hofstein, 2003). The main goal of this study was to assess the educational effectiveness of website activities dealing with the chemical bonding concept. These activities include visualization tools, as well as topics relevant to daily life and industrial applications. The study investigated the effectiveness of a web-based learning environment regarding the understanding of chemical bonding concepts, students' perceptions of the classroom learning environment, their attitudes regarding the relevance of learning chemistry to everyday life, and their interest in chemistry studies. As mentioned before, in the present study we focused on activities (from the website), all of which deal with chemical bonding concept. The following are the reasons for the decision to focus on this topic: (1) Chemical bonding is a key concept that is taught in 10th grade chemistry in high school. It provides the basis for many other chemistry topics that are taught later, and (2) Chemical bonding is a difficult for students using existing tools (e. g., static models in books, ball-and- stick models), which are insufficient to demonstrate the abstract nature phenomena associated with this topic. The four activities developed for this study are (1) models of the atomic structure, (2) metals -- structure and properties, (3) ionic substances in everyday life and in industry, and (4) molecular substances -- structure, properties, and uses. The study analyzed both quantitative and qualitative research. The quantitative tools of the study included: A Semantic Differential questionnaire and a Chemistry Classroom Web-Based Learning Environment

  15. Is There a Need to Discuss Atomic Orbital Overlap When Teaching Hydrogen-Halide Bond Strength and Acidity Trends in Organic Chemistry?

    Science.gov (United States)

    Devarajan, Deepa; Gustafson, Samantha J.; Bickelhaupt, F. Matthias; Ess, Daniel H.

    2015-01-01

    Undergraduate organic chemistry textbooks and Internet websites use a variety of approaches for presenting and explaining the impact of halogen atom size on trends in bond strengths and/or acidity of hydrogen halides. In particular, several textbooks and Internet websites explain these trends by invoking decreasing orbital overlap between the…

  16. Rapamycin selectively alters serum chemistry in diabetic mice

    Directory of Open Access Journals (Sweden)

    Hooman Tabatabai-Mir

    2012-04-01

    Full Text Available The study was undertaken to explore the effect of rapamycin, an anti-inflammatory agent, on the metabolic profile of type 2 diabetic mice. Seven-month-old diabetic db/db mice and their lean littermate non-diabetic controls (db/m were randomized to receive control chow or chow mixed with rapamycin (2.24 mg/kg/day (each group n =20, males and females for 4 months and sacrificed. Serum samples were analyzed for the measurement of glucose, creatinine, blood urea nitrogen (BUN, alkaline phosphatase (ALP, alanine aminotransferase (ALT, total cholesterol, total triglyceride, and total protein, using the automated dry chemistry analysis. Rapamycin elevated serum glucose in female diabetic mice. Serum creatinine tended to be higher in diabetic mice but was not affected by rapamycin; there was no difference in BUN levels among the groups. Serum ALP was elevated in diabetic mice and rapamycin lowered it only in female diabetic mice; serum ALT levels were increased in female diabetic mice, unaffected by rapamycin. Serum total protein was elevated in diabetic mice of both genders but was not affected by rapamycin. Diabetic mice from both genders had elevated serum cholesterol and triglycerides; rapamycin did not affect serum cholesterol but decreased serum total triglycerides in male diabetic mice. We conclude that rapamycin elicits complex metabolic responses in aging diabetic mice, worsening hyperglycemia in females but improving ALP in female diabetic and total triglycerides in male diabetic mice, respectively. The metabolic effects of rapamycin should be considered while performing studies with rapamycin in mice.

  17. Engineering novel cell surface chemistry for selective tumor cell targeting

    Energy Technology Data Exchange (ETDEWEB)

    Bertozzi, C.R. [Univ. of California, Berkeley, CA (United States)]|[Lawrence Berkeley National Lab., CA (United States)

    1997-12-31

    A common feature of many different cancers is the high expression level of the two monosaccharides sialic acid and fucose within the context of cell-surface associated glycoconjugates. A correlation has been made between hypersialylation and/or hyperfucosylation and the highly metastatic phenotype. Thus, a targeting strategy based on sialic acid or fucose expression would be a powerful tool for the development of new cancer cell-selective therapies and diagnostic agents. We have discovered that ketone groups can be incorporated metabolically into cell-surface associated sialic acids. The ketone is can be covalently ligated with hydrazide functionalized proteins or small molecules under physiological conditions. Thus, we have discovered a mechanism to selectively target hydrazide conjugates to highly sialylated cells such as cancer cells. Applications of this technology to the generation of novel cancer cell-selective toxins and MRI contrast reagents will be discussed, in addition to progress towards the use of cell surface fucose residues as vehicles for ketone expression.

  18. GREEN CHEMISTRY. Shape-selective zeolite catalysis for bioplastics production.

    Science.gov (United States)

    Dusselier, Michiel; Van Wouwe, Pieter; Dewaele, Annelies; Jacobs, Pierre A; Sels, Bert F

    2015-07-01

    Biodegradable and renewable polymers, such as polylactic acid, are benign alternatives for petrochemical-based plastics. Current production of polylactic acid via its key building block lactide, the cyclic dimer of lactic acid, is inefficient in terms of energy, time, and feedstock use. We present a direct zeolite-based catalytic process, which converts lactic acid into lactide. The shape-selective properties of zeolites are essential to attain record lactide yields, outperforming those of the current multistep process by avoiding both racemization and side-product formation. The highly productive process is strengthened by facile recovery and practical reactivation of the catalyst, which remains structurally fit during at least six consecutive reactions, and by the ease of solvent and side-product recycling. PMID:26138977

  19. GREEN CHEMISTRY. Shape-selective zeolite catalysis for bioplastics production.

    Science.gov (United States)

    Dusselier, Michiel; Van Wouwe, Pieter; Dewaele, Annelies; Jacobs, Pierre A; Sels, Bert F

    2015-07-01

    Biodegradable and renewable polymers, such as polylactic acid, are benign alternatives for petrochemical-based plastics. Current production of polylactic acid via its key building block lactide, the cyclic dimer of lactic acid, is inefficient in terms of energy, time, and feedstock use. We present a direct zeolite-based catalytic process, which converts lactic acid into lactide. The shape-selective properties of zeolites are essential to attain record lactide yields, outperforming those of the current multistep process by avoiding both racemization and side-product formation. The highly productive process is strengthened by facile recovery and practical reactivation of the catalyst, which remains structurally fit during at least six consecutive reactions, and by the ease of solvent and side-product recycling.

  20. The Origin of Bond Selectivity and Excited-State Reactivity in Retinal Analogues.

    Science.gov (United States)

    Schapiro, Igor

    2016-05-19

    The effect of different conformations and substitutions on the photoisomerization of a retinal protonated Schiff base model is investigated by nonadiabatic molecular dynamics simulations. Three groups of retinal analogues are studied: (i) conformational isomers, (ii) methyl-substituted retinals, and (iii) C11-C12 bond locked retinals. In total 259 trajectories are calculated in the gas phase starting from different initial conditions. The effect on bond selectivity, the directionality of the isomerization, excited-state lifetime, and product distribution is derived from the ensemble of trajectories. Among the group of four isomers (9-, 11-, 13-cis, and all-trans) the 11-cis analogue is the most selective in terms of isomerizing double bond, while the other three produce a mixture of isomers. However, there is no preference for isomerization directionality and the product formation for the 11-cis isomer. In the group of analogues with different methylation patterns, it is found that a methyl group at position C10 can introduce unidirectionality. This methyl group also speeds the photoisomerization. In case of the analogue that is demethylated at the positions C10 and C13, all trajectories isomerize successfully from cis to trans conformation. The three C11-C12 bond locked retinals are found to have very different properties, which depend on the number of methylene units bridging this bond. The five-membered ring imposes a too-large restriction; hence, all trajectories remain on the excited state in the simulation time of 300 fs. The seven-membered ring is more flexible with preference for isomerization of the C9-C10 bond. Interestingly, the eight-membered ring leads to the fastest isomerization time and full directionality of C11-C12 bond isomerization. The trends observed in these simulations can help to understand whether the effects are intrinsic to the chromophore or are induced by the protein environment, by comparing to the trends from experiment. Furthermore

  1. Chemistry

    International Nuclear Information System (INIS)

    The chemical research and development efforts related to the design and ultimate operation of molten-salt breeder reactor systems are concentrated on fuel- and coolant-salt chemistry, including the development of analytical methods for use in these systems. The chemistry of tellurium in fuel salt is being studied to help elucidate the role of this element in the intergranular cracking of Hastelloy N. Studies were continued of the effect of oxygen-containing species on the equilibrium between dissolved UF3 and dissolved UF4, and, in some cases, between the dissolved uranium fluorides and graphite, and the UC2. Several aspects of coolant-salt chemistry are under investigation. Hydroxy and oxy compounds that could be formed in molten NaBF4 are being synthesized and characterized. Studies of the chemistry of chromium (III) compounds in fluoroborate melts were continued as part of a systematic investigation of the corrosion of structural alloys by coolant salt. An in-line voltammetric method for determining U4+/U3+ ratios in fuel salt was tested in a forced-convection loop over a six-month period. (LK)

  2. Americium(3) coordination chemistry: An unexplored diversity of structure and bonding

    Energy Technology Data Exchange (ETDEWEB)

    Fedosseev, A.M.; Grigoriev, M.S.; Budantseva, N.A. [A.N. Frumkin Institute of Physical Chemistry and Electrochemistry, Moscow (Russian Federation); Guillaumont, D.; Den Auwer, Ch.; Moisy, Ph. [CEA Marcoule, Nuclear Energy Division, RadioChemistry and Processes Department, 30 (France); Le Naour, C.; Simoni, E. [CNRS, University Paris-11 Orsay, IPN, 91 - Orsay (France)

    2010-06-15

    The comparison of the physicochemical behavior of the actinides with that of the lanthanides can be justified by the analogy of their electronic structure, as each of the series is made up of elements corresponding to the filling of a given (n)f atomic shell. However relatively few points of comparison are available, given the lack of available structure for trans-plutonium(III) elements and the additional difficulty of stabilizing coordination complexes of uranium(III) to plutonium(III). This contribution is a focal point of trans-plutonium(III) chemistry and, more specifically, of some americium compounds that have been recently synthesized, all related with hard acid oxygen donor ligands that may be involved in the reprocessing chain of nuclear fuel. After a brief review of the solid hydrates and aquo species for the lanthanide and actinide families, we discuss two types of ligands that have in common three carboxylic groups, namely the amino-tri-acetic acid and the citric acid anions. The additional roles of the nitrogen atom for the first one and of the hydroxy function for the second one are discussed. Accordingly, five new complexes with either americium or lanthanides elements are described: [Co(NH{sub 3}){sub 6}][M(NTA){sub 2}(H{sub 2}O)].8H{sub 2}O with M Nd, Yb and Am, and [Co(NH{sub 3}){sub 6}]{sub 2}K[M{sub 3}(Cit){sub 4}(H{sub 2}O){sub 3}].18H{sub 2}O with Nd and Am cations. In all cases the americium complexes are isostructural with their lanthanide equivalents. (authors)

  3. Americium(3) coordination chemistry: An unexplored diversity of structure and bonding

    International Nuclear Information System (INIS)

    The comparison of the physicochemical behavior of the actinides with that of the lanthanides can be justified by the analogy of their electronic structure, as each of the series is made up of elements corresponding to the filling of a given (n)f atomic shell. However relatively few points of comparison are available, given the lack of available structure for trans-plutonium(III) elements and the additional difficulty of stabilizing coordination complexes of uranium(III) to plutonium(III). This contribution is a focal point of trans-plutonium(III) chemistry and, more specifically, of some americium compounds that have been recently synthesized, all related with hard acid oxygen donor ligands that may be involved in the reprocessing chain of nuclear fuel. After a brief review of the solid hydrates and aquo species for the lanthanide and actinide families, we discuss two types of ligands that have in common three carboxylic groups, namely the amino-tri-acetic acid and the citric acid anions. The additional roles of the nitrogen atom for the first one and of the hydroxy function for the second one are discussed. Accordingly, five new complexes with either americium or lanthanides elements are described: [Co(NH3)6][M(NTA)2(H2O)].8H2O with M Nd, Yb and Am, and [Co(NH3)6]2K[M3(Cit)4(H2O)3].18H2O with Nd and Am cations. In all cases the americium complexes are isostructural with their lanthanide equivalents. (authors)

  4. Bond-selective photoacoustic imaging by converting molecular vibration into acoustic waves.

    Science.gov (United States)

    Hui, Jie; Li, Rui; Phillips, Evan H; Goergen, Craig J; Sturek, Michael; Cheng, Ji-Xin

    2016-03-01

    The quantized vibration of chemical bonds provides a way of detecting specific molecules in a complex tissue environment. Unlike pure optical methods, for which imaging depth is limited to a few hundred micrometers by significant optical scattering, photoacoustic detection of vibrational absorption breaks through the optical diffusion limit by taking advantage of diffused photons and weak acoustic scattering. Key features of this method include both high scalability of imaging depth from a few millimeters to a few centimeters and chemical bond selectivity as a novel contrast mechanism for photoacoustic imaging. Its biomedical applications spans detection of white matter loss and regeneration, assessment of breast tumor margins, and diagnosis of vulnerable atherosclerotic plaques. This review provides an overview of the recent advances made in vibration-based photoacoustic imaging and various biomedical applications enabled by this new technology.

  5. Controllable synthesis of silver and silver sulfide nanocrystals via selective cleavage of chemical bonds

    International Nuclear Information System (INIS)

    A one-step colloidal process has been adopted to prepare silver (Ag) and silver sulfide (Ag2S) nanocrystals, thus avoiding presynthesis of an organometallic precursor and the injection of a toxic phosphine agent. During the reaction, a layered intermediate compound is first formed, which then acts as a precursor, decomposing into the nanocrystals. The composition of the as-obtained products can be controlled by selective cleavage of S–C bonds or Ag–S bonds. Pure Ag2S nanocrystals can be obtained by directly heating silver acetate (Ag(OAc)) and n-dodecanethiol (DDT) at 200 ° C without any surfactant, and pure Ag nanocrystals can be synthesized successfully if the reaction temperature is reduced to 190 ° C and the amount of DDT is decreased to 1 ml in the presence of a non-coordinating organic solvent (1-octadecene, ODE). Otherwise, the mixture of Ag and Ag2S is obtained by directly heating Ag(OAc) in DDT by increasing the reaction temperature or in a mixture of DDT and ODE at 200 ° C. The formation mechanism has been discussed in detail in terms of selective S–C and Ag–S bond dissociation due to the nucleophilic attack of DDT and the lower bonding energy of Ag–S. Interestingly, some products can easily self-assemble into two- or three-dimensional (2D or 3D) highly ordered superlattice structures on a copper grid without any additional steps. The excess DDT plays a key role in the superlattice structure due to the bundling and interdigitation of the thiolate molecules adsorbed on the as-obtained nanocrystals. (paper)

  6. Copper(I)-catalyzed carbon-halogen bond-selective boryl substitution of alkyl halides bearing terminal alkene moieties

    OpenAIRE

    Iwamoto, Hiroaki; Kubota, Koji; Yamamoto, Eiji; Ito, Hajime

    2015-01-01

    The selective boryl substitution of alkyl halides bearing terminal C=C double bonds has been achieved using a copper(I)/tricyclohexylphosphine or copper(I)/o-diphenylphosphinophenol catalyst. This reaction represents a useful complementary approach to conventional procedures for the hydroboration of C=C double bonds or the borylative cyclization of alkyl halides bearing terminal alkenes.

  7. Chemistry

    International Nuclear Information System (INIS)

    Research progress is reported in programs on fuel-salt chemistry, properties of compounds in the Li--Te system, Te spectroscopy UF4--H equilibria, porous electrode studies of molten salts, fuel salt-coolant salt reactions, thermodynamic properties of transition-metal fluorides, and properties of sodium fluoroborate. Developmental work on analytical methods is summarized including in-line analysis of molten MSBR fuel, analysis of coolant-salts for tritium, analysis of molten LiF--BeF2--ThF4 for Fe and analysis of LiF--BeF--ThF4 for Te

  8. Design and synthesis of multidentate ligands via metal promoted C-N bond formation processes and their coordination chemistry

    Indian Academy of Sciences (India)

    Kunal K Kamar; Amrita Saha; Sreebrata Goswami

    2002-08-01

    This presentation reports some novel examples of organic ring amination reactions via metal mediation. The organic transformations are highly regioselective and can be controlled by the proper selection of the mediator complex. The two isomeric organic ligands viz. HL1 and HL2 were isolated in their pure states by the removal of the metal ions. These were fully characterized. The ligand HL1 has low , 8.5. Upon deprotonation, it behaves as a potential bis chelating N,N,N-donors. The coordination chemistry of the HL1 ligand involving some 3-metal ions is described. Two unusual low-spin complexes of manganese(II) and iron(III) are reported. The ferric complex displayed a rhombic EPR while, the corresponding manganese compound showed a complex pattern due to hyperfine coupling. All the complexes displayed large number of redox responses. A brief mention about the future projection of this work is noted.

  9. Selective Access to Heterocyclic Sulfonamides and Sulfonyl Fluorides via a Parallel Medicinal Chemistry Enabled Method.

    Science.gov (United States)

    Tucker, Joseph W; Chenard, Lois; Young, Joseph M

    2015-11-01

    A sulfur-functionalized aminoacrolein derivative is used for the efficient and selective synthesis of heterocyclic sulfonyl chlorides, sulfonyl fluorides, and sulfonamides. The development of a 3-step parallel medicinal chemistry (PMC) protocol for the synthesis of pyrazole-4-sulfonamides effectively demonstrates the utility of this reagent. This reactivity was expanded to provide rapid access to other heterocyclic sulfonyl fluorides, including pyrimidines and pyridines, whose corresponding sulfonyl chlorides lack suitable chemical stability.

  10. Determining the Energetics of the Hydrogen Bond through FTIR: A Hands-On Physical Chemistry Lab Experiment

    Science.gov (United States)

    Guerin, Abby C.; Riley, Kristi; Rupnik, Kresimir; Kuroda, Daniel G.

    2016-01-01

    Hydrogen bonds are very important chemical structures that are responsible for many unique and important properties of solvents, such as the solvation power of water. These distinctive features are directly related to the stabilization energy conferred by hydrogen bonds to the solvent. Thus, the characterization of hydrogen bond energetics has…

  11. Chemistry of selected cyclic P(III) compounds possessing a P-Cl bond

    Indian Academy of Sciences (India)

    K C Kumara Swamy; Sudha Kumaraswamy; Praveen Kommana; N Satish Kumar; K Senthil Kumar

    2002-08-01

    The compounds [CH2(6--Bu-4-Me-C6H2O)2]PCl (1), (OCH2CMe2CH2O)-PCl (2), and [ClPN(-Bu)]2 (3) have been utilized as precursors in the synthesis of (i) new pentacoordinate phosphorus compounds [e.g. CH2(6--Bu-4-Me-C6H2O)2 P(NRR')(O2C6Cl4), CH2(6--Bu-4-Me-C6H2O)2PX[OC(O--Pr)N=N(C(O)O--Pr)], (ii) cyclic phosphates and their complexes [e.g. {imidazolium}+{CH2(6--Bu-4-Me-C6H2O)2PO2}-.MeOH], (iii) new cycloaddition products [e.g. {CH2(6--Bu-4-Me-C6H2O)2}P{C(CO2Me)C(CO2Me)C(O)N}, (iv) macrocyclic compounds [e.g. {[(-BuN)P]2[-OCH2CMe2CH2O-]}2] and (v) phosphonates [e.g. (OCH2CMe2CH2O)P (O)CH2C(CN)=CHC5H4FeC5H5]. The synthetic and structural aspects of these new products are discussed.

  12. Constitutional dynamic chemistry: bridge from supramolecular chemistry to adaptive chemistry.

    Science.gov (United States)

    Lehn, Jean-Marie

    2012-01-01

    Supramolecular chemistry aims at implementing highly complex chemical systems from molecular components held together by non-covalent intermolecular forces and effecting molecular recognition, catalysis and transport processes. A further step consists in the investigation of chemical systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined functional supramolecular architectures by self-assembly from their components, thus behaving as programmed chemical systems. Supramolecular chemistry is intrinsically a dynamic chemistry in view of the lability of the interactions connecting the molecular components of a supramolecular entity and the resulting ability of supramolecular species to exchange their constituents. The same holds for molecular chemistry when the molecular entity contains covalent bonds that may form and break reversibility, so as to allow a continuous change in constitution by reorganization and exchange of building blocks. These features define a Constitutional Dynamic Chemistry (CDC) on both the molecular and supramolecular levels.CDC introduces a paradigm shift with respect to constitutionally static chemistry. The latter relies on design for the generation of a target entity, whereas CDC takes advantage of dynamic diversity to allow variation and selection. The implementation of selection in chemistry introduces a fundamental change in outlook. Whereas self-organization by design strives to achieve full control over the output molecular or supramolecular entity by explicit programming, self-organization with selection operates on dynamic constitutional diversity in response to either internal or external factors to achieve adaptation.The merging of the features: -information and programmability, -dynamics and reversibility, -constitution and structural diversity, points to the emergence of adaptive and evolutive chemistry, towards a chemistry of complex matter.

  13. Intrinsic Folding Proclivities in Cyclic β-Peptide Building Blocks: Configuration and Heteroatom Effects Analyzed by Conformer-Selective Spectroscopy and Quantum Chemistry.

    Science.gov (United States)

    Alauddin, Mohammad; Gloaguen, Eric; Brenner, Valérie; Tardivel, Benjamin; Mons, Michel; Zehnacker-Rentien, Anne; Declerck, Valérie; Aitken, David J

    2015-11-01

    This work describes the use of conformer-selective laser spectroscopy following supersonic expansion to probe the local folding proclivities of four-membered ring cyclic β-amino acid building blocks. Emphasis is placed on stereochemical effects as well as on the structural changes induced by the replacement of a carbon atom of the cycle by a nitrogen atom. The amide A IR spectra are obtained and interpreted with the help of quantum chemistry structure calculations. Results provide evidence that the building block with a trans-substituted cyclobutane ring has a predilection to form strong C8 hydrogen bonds. Nitrogen-atom substitution in the ring induces the formation of the hydrazino turn, with a related but distinct hydrogen-bonding network: the structure is best viewed as a bifurcated C8/C5 bond with the N heteroatom lone electron pair playing a significant acceptor role, which supports recent observations on the hydrazino turn structure in solution. Surprisingly, this study shows that the cis-substituted cyclobutane ring derivative also gives rise predominantly to a C8 hydrogen bond, although weaker than in the two former cases, a feature that is not often encountered for this building block.

  14. Photoisomerization selectivity in conjugated π-bond systems through local microenvironment

    Science.gov (United States)

    Virshup, Aaron; Martinez, Todd

    2007-03-01

    Photoisomerization represents one of the simplest means to convert light energy into mechanical motion on the molecular scale. Theoretical models of photobiology often require description of not only a small photochemically active chromophore, but also the effects of the much larger solvent or protein environment containing the chromophore. We have recently developed a program for carrying out excited state QM/MM studies of photodynamics using ab initio quantum chemistry techniques for the QM region, and modeling the time evolution of the system with the Full Multiple Spawning method for molecular dynamics. With this method, we show how local charge environments can be used to manipulate and enhance the photoisomer selectivity of small conjugated molecules.

  15. Chemistry

    International Nuclear Information System (INIS)

    Research and development activities dealing with the chemical problems related to design and ultimate operation of molten-salt reactor systems are described. An experimental test stand was constructed to expose metallurgical test specimens to Te2 vapor at defined temperatures and deposition rates. To better define the chemistry of fluoroborate coolant, several aspects are being investigated. The behavior of hydroxy and oxy compounds in molten NaBF4 is being investigated to define reactions and compounds that may be involved in corrosion and/or could be involved in methods for trapping tritium. Two corrosion products of Hastelloy N, Na3CrF6 and Na5Cr3F14, were identified from fluoroborate systems. The evaluation of fluoroborate and alternate coolants continued. Research on the behavior of hydrogen and its isotopes is summarized. The solubilities of hydrogen, deuterium, and helium in Li2BeF4 are very low. The sorption of tritium on graphite was found to be significant (a few milligrams of tritium per kilogram of graphite), possibly providing a means of sequestering a portion of the tritium produced. Development of analytical methods continued with emphasis on voltammetric and spectrophotometric techniques for the in-line analysis of corrosion products such as Fe2+ and Cr3+ and the determination of the U3+/U4+ ratio in MSBR fuel salt. Similar studies were conducted with the NaBF4--NaF coolant salt. Information developed during the previous operation of the CSTF has been assessed and used to formulate plans for evaluation of in-line analytical methods in future CSTF operations. Electroanalytical and spectrophotometric research suggests that an electroactive protonic species is present in molten NaBF4--NaF, and that this species rapidly equilibrates with a volatile proton-containing species. Data obtained from the CSTF indicated that tritium was concentrated in the volatile species. (JGB)

  16. Metal Nanoparticles Catalyzed Selective Carbon-Carbon Bond Activation in the Liquid Phase.

    Science.gov (United States)

    Ye, Rong; Yuan, Bing; Zhao, Jie; Ralston, Walter T; Wu, Chung-Yeh; Unel Barin, Ebru; Toste, F Dean; Somorjai, Gabor A

    2016-07-13

    Understanding the C-C bond activation mechanism is essential for developing the selective production of hydrocarbons in the petroleum industry and for selective polymer decomposition. In this work, ring-opening reactions of cyclopropane derivatives under hydrogen catalyzed by metal nanoparticles (NPs) in the liquid phase were studied. 40-atom rhodium (Rh) NPs, encapsulated by dendrimer molecules and supported in mesoporous silica, catalyzed the ring opening of cyclopropylbenzene at room temperature under hydrogen in benzene, and the turnover frequency (TOF) was higher than other metals or the Rh homogeneous catalyst counterparts. Comparison of reactants with various substitution groups showed that electron donation on the three-membered ring boosted the TOF of ring opening. The linear products formed with 100% selectivity for ring opening of all reactants catalyzed by the Rh NP. Surface Rh(0) acted as the active site in the NP. The capping agent played an important role in the ring-opening reaction kinetics. Larger particle size tended to show higher TOF and smaller reaction activation energy for Rh NPs encapsulated in either dendrimer or poly(vinylpyrrolidone). The generation/size of dendrimer and surface group also affected the reaction rate and activation energy. PMID:27322570

  17. Size-selective fractionation and visual mapping of allergen protein chemistry in Arachis hypogaea.

    Science.gov (United States)

    Hebling, Christine M; Ross, Mark M; Callahan, John H; McFarland, Melinda A

    2012-11-01

    Peanuts (Arachis hypogaea) in addition to milk, eggs, fish, crustaceans, wheat, tree nuts, and soybean are commonly referred to as the "big eight" foods that contribute to the majority of food allergies worldwide. Despite the severity of allergic reactions and growing prevalence in children and adults, there is no cure for peanut allergy, leaving avoidance as the primary mode of treatment. To improve analytical methods for peanut allergen detection, researchers must overcome obstacles involved in handling complex food matrices while attempting to decipher the chemistry that underlies allergen protein interactions. To address such challenges, we conducted a global proteome characterization of raw peanuts using a sophisticated GELFrEE-PAGE-LC-MS/MS platform consisting of gel-based protein fractionation followed by mass spectrometric identification. The in-solution mass-selective protein fractionation: (1) enhances the number of unique peptide identifications, (2) provides a visual map of protein isoforms, and (3) aids in the identification of disulfide-linked protein complexes. GELFrEE-PAGE-LC-MS/MS not only overcomes many of the challenges involved in the study of plant proteomics, but enriches the understanding of peanut protein chemistry, which is typically unattainable in a traditional bottom-up proteomic analysis. A global understanding of protein chemistry in Arachis hypogaea ultimately will aid the development of improved methods for allergen detection in food. PMID:23020697

  18. The Novel Selective Reduction of the C-C Triple Bond

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    A novel reduction system is reported here in which the compounds with terminal C-C triple bond and disubstituted C-C triple bond react with NaBH4/Pd(PPh3)4 in a base condition and only terminal C-C triple bond is reduced.

  19. Conceptual chemistry approach towards the support effect in supported vanadium oxides : Valence bond calculations on the ionicity of vanadium catalysts

    NARCIS (Netherlands)

    Fievez, Tim; De Proft, Frank; Geerlings, Paul; Weckhuysen, Bert M.; Havenith, Remco W. A.

    2011-01-01

    The concept of bond ionicity, obtained via a valence bond analysis, is invoked in the interpretation of the catalytic activity of supported vanadium oxides, in analogy with previous work conducted within the framework of conceptual DFT. For a set of model clusters representing the vanadium oxide sup

  20. Building chemistry one atom at a time: An investigation of the effects of two curricula in students' understanding of covalent bonding and atomic size

    Science.gov (United States)

    Bull, Barbara Jeanne

    Chemists have to rely on models to aid in the explanation of phenomena they experience. Instruction of atomic theory has been used as the introduction and primary model for many concepts in chemistry. Therefore, it is important for students to have a robust understanding of the different atomic models, their relationships and their limitations. Previous research has shown that students have alternative conceptions concerning their interpretation of atomic models, but there is less exploration into how students apply their understanding of atomic structure to other chemical concepts. Therefore, this research concentrated on the development of three Model Eliciting Activities to investigate the most fundamental topic of the atom and how students applied their atomic model to covalent bonding and atomic size. Along with the investigation into students' use of their atomic models, a comparison was included between a traditional chemistry curriculum using an Atoms First approach and Chemistry, Life, the Universe and Everything (CLUE), a NSF-funded general chemistry curriculum. Treatment and Control groups were employed to determine the effectiveness of the curricula in conveying the relationship between atoms, covalent bonds and atomic size. The CLUE students developed a Cloud representation on the Atomic Model Eliciting Activity and maintained this depiction through the Covalent Bonding Model Eliciting Activity. The traditional students more often illustrated the atom using a Bohr representation and continued to apply the same model to their portrayal of covalent bonding. During the analysis of the Atomic Size Model Eliciting Activity, students had difficulty fully supporting their explanation of the atomic size trend. Utilizing the beSocratic platform, an activity was designed to aid students' construction of explanations using Toulmin's Argumentation Pattern. In order to study the effectiveness of the activity, the students were asked questions relating to a four

  1. Enhanced Control of PWR Primary Coolant Water Chemistry Using Selective Separation Systems for Recovery and Recycle of Enriched Boric Acid

    Energy Technology Data Exchange (ETDEWEB)

    Ken Czerwinski; Charels Yeamans; Don Olander; Kenneth Raymond; Norman Schroeder; Thomas Robison; Bryan Carlson; Barbara Smit; Pat Robinson

    2006-02-28

    The objective of this project is to develop systems that will allow for increased nuclear energy production through the use of enriched fuels. The developed systems will allow for the efficient and selective recover of selected isotopes that are additives to power water reactors' primary coolant chemistry for suppression of corrosion attack on reactor materials.

  2. Selected legal aspects of mortgage bonds in European law, with emphasis on German legislation

    OpenAIRE

    Sieradzki, Jakub

    2011-01-01

    The article discusses the German legislation in relation to mortgage bonds, and also briefly describes the state of European legislation in this regard. There are also themes from other countries in which such mortgage bonds are used. The publication consists of 5 sections, where the first is the introduction and the last contains the conclusions. The main part of the article is part 4, where the author briefly discusses the German Law on Mortgage Bonds. Parts 2 and 3 are the legal background...

  3. Quantum dynamics of polyatomic dissociative chemisorption on transition metal surfaces: mode specificity and bond selectivity.

    Science.gov (United States)

    Jiang, Bin; Yang, Minghui; Xie, Daiqian; Guo, Hua

    2016-06-27

    Dissociative chemisorption is the initial and often rate-limiting step in many heterogeneous processes. As a result, an in-depth understanding of the reaction dynamics of such processes is of great importance for the establishment of a predictive model of heterogeneous catalysis. Overwhelming experimental evidence has suggested that these processes have a non-statistical nature and excitations in various reactant modes have a significant impact on reactivity. A comprehensive characterization of the reaction dynamics requires a quantum mechanical treatment on a global potential energy surface. In this review, we summarize recent progress in constructing high-dimensional potential energy surfaces for polyatomic molecules interacting with transition metal surfaces based on the plane-wave density functional theory and in quantum dynamical studies of dissociative chemisorption on these potential energy surfaces. A special focus is placed on the mode specificity and bond selectivity in these gas-surface collisional processes, and their rationalization in terms of the recently proposed Sudden Vector Projection model. PMID:26100606

  4. Selectively bonded polymeric glaucoma drainage device for reliable regulation of intraocular pressure.

    Science.gov (United States)

    Moon, Seunghwan; Im, Seongmin; An, Jaeyong; Park, Chang Ju; Kim, Hwang Gyun; Park, Sang Woo; Kim, Hyoung Ihl; Lee, Jong-Hyun

    2012-04-01

    A novel glaucoma drainage device (GDD) using a polymeric micro check valve with no reverse flow is presented for the effective regulation of intraocular pressure (IOP). A significant functional improvement was achieved by reducing the possible incidence of hypotony, as the proposed GDD only drains aqueous humor at a certain cracking pressure or higher. The device consists of three biocompatible polymer layers: a top layer (cover), an intermediate layer (membrane), and a bottom layer (base plate with a cannula). All three layers, made of soft polydimethylsiloxane (PDMS), were bonded together to realize the thin GDDs. The bottom layer was selectively coated with chromium (Cr)/gold (Au) to prevent stiction between the valve seat and the valve orifice so that the device could show enhanced reliability in operation and high yield in production. Two types of polymeric devices were fabricated; one was a glaucoma drainage device for humans (GDDH) and the other was a glaucoma drainage device for animals (GDDA). From subsequent in vitro tests, the cracking pressures were 18.33 ± 0.66 mmHg (mean ± standard deviation) for GDDH and 12.42 mmHg for GDDA, both of which were very close to the corresponding normal IOPs. From in vivo tests of GDDA, the IOP of all implanted devices was properly regulated within the target pressure (10-15 mmHg). The experimental results showed that the proposed polymeric GDD has high potential for use in the treatment of glaucoma disease in terms of its repeatability of the cracking pressure and patients' relief from post-operative discomfort. PMID:22094823

  5. Infrared and Raman spectroscopy and quantum chemistry calculation studies of C H⋯O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoate

    Science.gov (United States)

    Sato, Harumi; Dybal, Jiří; Murakami, Rumi; Noda, Isao; Ozaki, Yukihiro

    2005-06-01

    This review paper reports infrared (IR) and Raman spectroscopy and quantum chemistry calculation studies of C-H⋯O hydrogen bondings and thermal behavior of biodegradable polyhydroxyalkanoates. IR and Raman spectra were measured for poly(3-hydroxybutyrate) (PHB) and a new type of bacterial copolyester, poly(3-hydroxybutyrate- co-3-hydroxyhexanoate), P(HB- co-HHx) (HHx=12 mol%) over a temperature range of 20 °C to higher temperatures (PHB, 200 °C; HHx=12 mol%, 140 °C) to explore their structure and thermal behavior. One of bands due to the CH 3 asymmetric stretching modes appears near 3010 cm -1 in the IR and Raman spectra of PHB and P(HB- co-HHx) at 20 °C. These frequencies of IR and Raman CH 3 asymmetric stretching bands are much higher than usual. These anomalous frequencies of the CH 3 asymmetric stretching bands together with the X-ray crystallographic structure of PHB have suggested that there is an inter- or intra-molecular C-H⋯O hydrogen bond between the C dbnd6 O group in one helical structure and the CH 3 group in the other helical structure in PHB and P(HB- co-HHx). The quantum chemical calculation of model compounds of PHB also has suggested the existence of C-H⋯O hydrogen bonds in PHB and P(HB- co-HHx). It is very likely that a chain of C-H⋯O hydrogen bond pairs link two parallel helical structures in the crystalline parts. The temperature-dependent IR and Raman spectral variations have revealed that the crystallinity of P(HB- co-HHx) (HHx=12 mol%) decreases gradually from a fairly low temperature (about 60 °C), while the crystallinity of PHB remains almost unchanged until just below its melting temperature. It has also been found from the IR and Raman studies that for both PHB and P(HB- co-HHx) the weakening of the C-H⋯O hydrogen bonds starts from just above room temperature, but the deformation of helical structures occurs after the weakening of the C-H⋯O hydrogen bonds advances to some extent.

  6. Organic chemistry

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2003-08-15

    This book with sixteen chapter explains organic chemistry on linkage isomerism such as alkane, cycloalkane, alkene, aromatic compounds, stereo selective isomerization, aromatic compounds, stereo selective isomerization, organic compounds, stereo selective isomerization, organic halogen compound, alcohol, ether, aldehyde and ketone, carboxylic acid, dicarboxylic acid, fat and detergent, amino, carbohydrate, amino acid and protein, nucleotide and nucleic acid and spectroscopy, a polymer and medical chemistry. Each chapter has introduction structure and characteristic and using of organic chemistry.

  7. Application of Radiation Chemistry to Some Selected Technological Issues Related to the Development of Nuclear Energy.

    Science.gov (United States)

    Bobrowski, Krzysztof; Skotnicki, Konrad; Szreder, Tomasz

    2016-10-01

    The most important contributions of radiation chemistry to some selected technological issues related to water-cooled reactors, reprocessing of spent nuclear fuel and high-level radioactive wastes, and fuel evolution during final radioactive waste disposal are highlighted. Chemical reactions occurring at the operating temperatures and pressures of reactors and involving primary transients and stable products from water radiolysis are presented and discussed in terms of the kinetic parameters and radiation chemical yields. The knowledge of these parameters is essential since they serve as input data to the models of water radiolysis in the primary loop of light water reactors and super critical water reactors. Selected features of water radiolysis in heterogeneous systems, such as aqueous nanoparticle suspensions and slurries, ceramic oxides surfaces, nanoporous, and cement-based materials, are discussed. They are of particular concern in the primary cooling loops in nuclear reactors and long-term storage of nuclear waste in geological repositories. This also includes radiation-induced processes related to corrosion of cladding materials and copper-coated iron canisters, dissolution of spent nuclear fuel, and changes of bentonite clays properties. Radiation-induced processes affecting stability of solvents and solvent extraction ligands as well oxidation states of actinide metal ions during recycling of the spent nuclear fuel are also briefly summarized.

  8. Application of Radiation Chemistry to Some Selected Technological Issues Related to the Development of Nuclear Energy.

    Science.gov (United States)

    Bobrowski, Krzysztof; Skotnicki, Konrad; Szreder, Tomasz

    2016-10-01

    The most important contributions of radiation chemistry to some selected technological issues related to water-cooled reactors, reprocessing of spent nuclear fuel and high-level radioactive wastes, and fuel evolution during final radioactive waste disposal are highlighted. Chemical reactions occurring at the operating temperatures and pressures of reactors and involving primary transients and stable products from water radiolysis are presented and discussed in terms of the kinetic parameters and radiation chemical yields. The knowledge of these parameters is essential since they serve as input data to the models of water radiolysis in the primary loop of light water reactors and super critical water reactors. Selected features of water radiolysis in heterogeneous systems, such as aqueous nanoparticle suspensions and slurries, ceramic oxides surfaces, nanoporous, and cement-based materials, are discussed. They are of particular concern in the primary cooling loops in nuclear reactors and long-term storage of nuclear waste in geological repositories. This also includes radiation-induced processes related to corrosion of cladding materials and copper-coated iron canisters, dissolution of spent nuclear fuel, and changes of bentonite clays properties. Radiation-induced processes affecting stability of solvents and solvent extraction ligands as well oxidation states of actinide metal ions during recycling of the spent nuclear fuel are also briefly summarized. PMID:27573502

  9. Crystal chemistry of sartorite homologues and related sulfosalts

    DEFF Research Database (Denmark)

    Berlepsch, Peter; Makovicky, Emil; Balic-Zunic, Tonci

    2001-01-01

    sartorite homologues, sulfosalt, crystal chemistry, coordination polyhedra, bond-pairs, crankshaft chains......sartorite homologues, sulfosalt, crystal chemistry, coordination polyhedra, bond-pairs, crankshaft chains...

  10. Selective Bifunctional Modification of a Non-catenated Metal-Organic Framework Material via 'Click' Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Gadzikwa, Tendai; Farha, Omar K.; Malliakas, Christos D.; Kanatzidis, Mercouri G.; Hupp, Joseph T.; Nguyen, SonBinh T.; NWU

    2009-12-01

    A noncatenated, Zn-based metal-organic framework (MOF) material bearing silyl-protected acetylenes was constructed and postsynthetically modified using 'click' chemistry. Using a solvent-based, selective deprotection strategy, two different organic azides were 'clicked' onto the MOF crystals, resulting in a porous material whose internal and external surfaces are differently functionalized.

  11. Environmental carbonate chemistry selects for phenotype of recently isolated strains of Emiliania huxleyi

    Science.gov (United States)

    Rickaby, Rosalind E. M.; Hermoso, Michaël; Lee, Renee B. Y.; Rae, Benjamin D.; Heureux, Ana M. C.; Balestreri, Cecilia; Chakravarti, Leela; Schroeder, Declan C.; Brownlee, Colin

    2016-05-01

    Coccolithophorid algae, particularly Emiliania huxleyi, are prolific biomineralisers that, under many conditions, dominate communities of marine eukaryotic plankton. Their ability to photosynthesise and form calcified scales (coccoliths) has placed them in a unique position in the global carbon cycle. Contrasting reports have been made with regards to the response of E. huxleyi to ocean acidification. Therefore, there is a pressing need to further determine the fate of this key organism in a rising CO2 world. In this paper, we investigate the phenotype of newly isolated, genetically diverse, strains of E. huxleyi from UK Ocean Acidification Research Programme (UKOA) cruises around the British Isles, the Arctic, and the Southern Ocean. We find a continuum of diversity amongst the physiological and photosynthetic parameters of different strains of E. huxleyi morphotype A under uniform, ambient conditions imposed in the laboratory. This physiology is best explained by adaptation to carbonate chemistry in the former habitat rather than being prescribed by genetic fingerprints such as the coccolithophore morphology motif (CMM). To a first order, the photosynthetic capacity of each strain is a function of both aqueous CO2 availability, and calcification rate, suggestive of a link between carbon concentrating ability and calcification. The calcification rate of each strain is related linearly to the natural environmental [CO32-] at the site of isolation, but a few exceptional strains display low calcification rates at the highest [CO32-] when calcification is limited by low CO2 availability and/or a lack of a carbon concentrating mechanism. We present O2-electrode measurements alongside coccolith oxygen isotopic composition and the uronic acid content (UAC) of the coccolith associated polysaccharide (CAP), that act as indirect tools to show the differing carbon concentrating ability of the strains. The environmental selection revealed amongst our recently isolated strain

  12. Frontiers in Gold Chemistry

    OpenAIRE

    Mohamed, Ahmed A.

    2015-01-01

    Basic chemistry of gold tells us that it can bond to sulfur, phosphorous, nitrogen, and oxygen donor ligands. The Frontiers in Gold Chemistry Special Issue covers gold complexes bonded to the different donors and their fascinating applications. This issue covers both basic chemistry studies of gold complexes and their contemporary applications in medicine, materials chemistry, and optical sensors. There is a strong belief that aurophilicity plays a major role in the unending applications of g...

  13. Chemistry {ampersand} Materials Science progress report summary of selected research and development topics, FY97

    Energy Technology Data Exchange (ETDEWEB)

    Newkirk, L.

    1997-12-01

    This report contains summaries of research performed in the Chemistry and Materials Science division. Topics include Metals and Ceramics, High Explosives, Organic Synthesis, Instrument Development, and other topics.

  14. Major-ion and selected trace-metal chemistry of the Biscayne Aquifer, Southeast Florida

    Science.gov (United States)

    Radell, M.J.; Katz, B.G.

    1991-01-01

    The major-ion and selected trace-metal chemistry of the Biscayne aquifer was characterized as part of the Florida Ground-Water Quality Monitoring Network Program, a multiagency cooperative effort concerned with delineating baseline water quality for major aquifer systems in the State. The Biscayne aquifer is unconfined and serves as the sole source of drinking water for more than 3 million people in southeast Florida. The Biscayne aquifer consists of highly permeable interbedded limestone and sandstone of Pleistocene and Pliocene age underlying most of Dade and Broward Counties and parts of Palm Beach and Monroe Counties. The high permeability is largely caused by extensive carbonate dissolution. Water sampled from 189 wells tapping the Biscayne aquifer was predominantly a calcium bicarbonate type with some mixed types occurring in coastal areas and near major canals. Major - ion is areally uniform throughout the aquifer. According to nonparametric statistical tests of major ions and dissolved solids, the concentrations of calcium, sodium, bicarbonate, and dissolved solids increased significantly with well depth ( 0.05 significance level ), probably a result of less circulation at depth. Potassium and nitrate concentrations decreased significantly with depth. Although the source of recharge to the aquifer varies seasonally, there was no statistical difference in the concentration of major ions in pared water samples from 27 shallow wells collected during wet and dry seasons. Median concentrations for barium, chromium, copper, lead, and manganese were below maximum or secondary maximum contaminant levels set by the US Environmental Protection Agency. The median iron concentration only slightly exceeded the secondary maximum contaminant level. The concentration of barium was significantly related (0.05 significance level) to calcium and bicarbonate concentration. No distinct areal pattern or vertical distribution of the selected trace metals was evident in water from

  15. Reductive cleavage of dichalcogenide bonds. Communication 3. Selectivity of electron exchange in diaryldichalcogenide-bispyridinium systems

    International Nuclear Information System (INIS)

    The kinetics of reductive cleavage of the dichalcogenide bond in dimeric Schiff's bases ArEEAr (E = S, Te) induced by indirect electron transfer by the in situ generated bridged bispyridinium radical cations and biradicals was studied by cyclic voltammetry. It is found that the dependence between the apparent rate constants of intermolecular electron transfer and the electron-withdrawing properties of diaryldichalcogenides is violated. The mechanisms of homogeneous (chemical) and heterogeneous (electrochemical) reductive cleavage of diaryldichalcogenides are discussed

  16. Organometallic chemistry

    OpenAIRE

    Bashkin, James K.; M.L.H. Green; Dr. M. L. H. Green

    1982-01-01

    Transition metal organometallic chemistry is a rapidly expanding field, which has an important relationship to industrial problems of petrochemical catalysis. This thesis describes studies of fundamental organometallic reaction processes, such as C-H and C-C bond formation and cleavage, and investigations of the structure and bonding of organometallic compounds. A number of techniques were used to pursue these studies, including synthesis, X-ray crystallography, and semi-em...

  17. A Systematic Study of Structure and E-H Bond Activation Chemistry by Sterically Encumbered Germylene Complexes.

    Science.gov (United States)

    Usher, Matthew; Protchenko, Andrey V; Rit, Arnab; Campos, Jesús; Kolychev, Eugene L; Tirfoin, Rémi; Aldridge, Simon

    2016-08-01

    A series of new germylene compounds has been synthesized offering systematic variation in the σ- and π-capabilities of the α-substituent and differing levels of reactivity towards E-H bond activation (E=H, B, C, N, Si, Ge). Chloride metathesis utilizing [(terphenyl)GeCl] proves to be an effective synthetic route to complexes of the type [(terphenyl)Ge(ERn )] (1-6: ERn =NHDipp, CH(SiMe3 )2 , P(SiMe3 )2 , Si(SiMe3 )3 or B(NDippCH)2 ; terphenyl=C6 H3 Mes2 -2,6=Ar(Mes) or C6 H3 Dipp2 -2,6=Ar(Dipp) ; Dipp=C6 H3 iPr2 -2,6, Mes=C6 H2 Me3 -2,4,6), while the related complex [{(Me3 Si)2 N}Ge{B(NDippCH)2 }] (8) can be accessed by an amide/boryl exchange route. Metrical parameters have been probed by X-ray crystallography, and are consistent with widening angles at the metal centre as more bulky and/or more electropositive substituents are employed. Thus, the widest germylene units (θ>110°) are found to be associated with strongly σ-donating boryl or silyl ancillary donors. HOMO-LUMO gaps for the new germylene complexes have been appraised by DFT calculations. The aryl(boryl)-germylene system [Ar(Mes) Ge{B(NDippCH)2 }] (6-Mes), which features a wide C-Ge-B angle (110.4(1)°) and (albeit relatively weak) ancillary π-acceptor capabilities, has the smallest HOMO-LUMO gap (119 kJ mol(-1) ). These features result in 6-Mes being remarkably reactive, undergoing facile intramolecular C-H activation involving one of the mesityl ortho-methyl groups. The related aryl(silyl)-germylene system, [Ar(Mes) Ge{Si(SiMe3 )3 }] (5-Mes) has a marginally wider HOMO-LUMO gap (134 kJ mol(-1) ), rendering it less labile towards decomposition, yet reactive enough to oxidatively cleave H2 and NH3 to give the corresponding dihydride and (amido)hydride. Mixed aryl/alkyl, aryl/amido and aryl/phosphido complexes are unreactive, but amido/boryl complex 8 is competent for the activation of E-H bonds (E=H, B, Si) to give hydrido, boryl and silyl products. The results of these reactivity studies

  18. Students' Visualization of Metallic Bonding and the Malleability of Metals

    Science.gov (United States)

    Cheng, Maurice M. W.; Gilbert, John K.

    2014-01-01

    This study investigated the mental representations of metallic bonding and the malleability of metals held by three male students aged 14-15 (Year 10) who were attending a Hong Kong school. One student was selected by their chemistry teacher as representing each of the highest, the medium, and the lowest level of attainment in chemistry in a…

  19. Selective Oxidative Decarbonylative Cleavage of Unstrained C(sp(3))-C(sp(2)) Bond: Synthesis of Substituted Benzoxazinones.

    Science.gov (United States)

    Verma, Ajay; Kumar, Sangit

    2016-09-01

    A transition metal (TM)-free practical synthesis of biologically relevant benzoxazinones has been established via a selective oxidative decarbonylative cleavage of an unstrained C(sp(3))-C(sp(2)) bond employing iodine, sodium bicarbonate, and (t)butyl hydroperoxide in DMSO at 95 °C. Control experiments and Density Functional Theory (DFT) calculations suggest that the reaction involves a [1,5]H shift and extrusion of CO gas as the key steps. The extrusion of CO has also been established using PMA-PdCl2. PMID:27549986

  20. Solvent-Free Selective Condensations Based on the Formation of the Olefinic (C=C Bond Catalyzed by Organocatalyst

    Directory of Open Access Journals (Sweden)

    Heyuan Song

    2016-07-01

    Full Text Available Pyrrolidine and its derivatives were used to catalyze aldol and Knoevenagel condensations for the formation of the olefinic (C=C bond under solvent-free conditions. The 3-pyrrolidinamine showed high activity and afforded excellent yields of α,β-unsaturated compounds. The aldol condensation of aromatic/heterocyclic aldehydes with ketones affords enones in high conversion (99.5% and selectivity (92.7%. Good to excellent yields of α,β-unsaturated compounds were obtained in the Knoevenagel condensation of aldehydes with methylene-activated substrates.

  1. Direct Construction of 4-Hydroxybenzils via Para-Selective C-C Bond Coupling of Phenols and Aryl Methyl Ketones.

    Science.gov (United States)

    Xiang, Jia-Chen; Cheng, Yan; Wang, Miao; Wu, Yan-Dong; Wu, An-Xin

    2016-09-01

    A highly para-selective C-C bond coupling is presented between phenols C(sp(2)) and aryl methyl ketones C(sp(3)), which enables the direct construction of 4-hydroxybenzil derivatives. This practical method exhibits a broad substrate scope and large-scale applicability and represents a general gateway to the hydroxybenzil natural product family. Mechanistic investigations indicated that the combination of HI with DMSO realized the oxidative carbonylation of aryl methyl ketones, while boric acid acted as a dual-functional relay reagent to promote this transformation. PMID:27513164

  2. Combining Chemistry and Music to Engage Student Interest: Using Songs to Accompany Selected Chemical Topics

    Science.gov (United States)

    Last, Arthur M.

    2009-01-01

    The use of recorded music to add interest to a variety of lecture topics is described. Topics include the periodic table, the formation of ionic compounds, thermodynamics, carbohydrates, nuclear chemistry, and qualitative analysis. (Contains 1 note.)

  3. Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications.

    Science.gov (United States)

    Vaithilingam, Jayasheelan; Prina, Elisabetta; Goodridge, Ruth D; Hague, Richard J M; Edmondson, Steve; Rose, Felicity R A J; Christie, Steven D R

    2016-10-01

    Selective laser melting (SLM) has previously been shown to be a viable method for fabricating biomedical implants; however, the surface chemistry of SLM fabricated parts is poorly understood. In this study, X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemistries of (a) SLM as-fabricated (SLM-AF) Ti6Al4V and (b) SLM fabricated and mechanically polished (SLM-MP) Ti6Al4V samples and compared with (c) traditionally manufactured (forged) and mechanically polished Ti6Al4V samples. The SLM-AF surface was observed to be porous with an average surface roughness (Ra) of 17.6±3.7μm. The surface chemistry of the SLM-AF was significantly different to the FGD-MP surface with respect to elemental distribution and their existence on the outermost surface. Sintered particles on the SLM-AF surface were observed to affect depth profiling of the sample due to a shadowing effect during argon ion sputtering. Surface heterogeneity was observed for all three surfaces; however, vanadium was witnessed only on the mechanically polished (SLM-MP and FGD-MP) surfaces. The direct and indirect 3T3 cell cytotoxicity studies revealed that the cells were viable on the SLM fabricated Ti6Al4V parts. The varied surface chemistry of the SLM-AF and SLM-MP did not influence the cell behaviour.

  4. Surface chemistry of Ti6Al4V components fabricated using selective laser melting for biomedical applications.

    Science.gov (United States)

    Vaithilingam, Jayasheelan; Prina, Elisabetta; Goodridge, Ruth D; Hague, Richard J M; Edmondson, Steve; Rose, Felicity R A J; Christie, Steven D R

    2016-10-01

    Selective laser melting (SLM) has previously been shown to be a viable method for fabricating biomedical implants; however, the surface chemistry of SLM fabricated parts is poorly understood. In this study, X-ray photoelectron spectroscopy (XPS) was used to determine the surface chemistries of (a) SLM as-fabricated (SLM-AF) Ti6Al4V and (b) SLM fabricated and mechanically polished (SLM-MP) Ti6Al4V samples and compared with (c) traditionally manufactured (forged) and mechanically polished Ti6Al4V samples. The SLM-AF surface was observed to be porous with an average surface roughness (Ra) of 17.6±3.7μm. The surface chemistry of the SLM-AF was significantly different to the FGD-MP surface with respect to elemental distribution and their existence on the outermost surface. Sintered particles on the SLM-AF surface were observed to affect depth profiling of the sample due to a shadowing effect during argon ion sputtering. Surface heterogeneity was observed for all three surfaces; however, vanadium was witnessed only on the mechanically polished (SLM-MP and FGD-MP) surfaces. The direct and indirect 3T3 cell cytotoxicity studies revealed that the cells were viable on the SLM fabricated Ti6Al4V parts. The varied surface chemistry of the SLM-AF and SLM-MP did not influence the cell behaviour. PMID:27287125

  5. Bond-selective fragmentation of water molecules with intense, ultrafast, carrier envelope phase stabilized laser pulses

    CERN Document Server

    Mathur, D; Dharmadhikari, J A; Dharmadhikari, A K

    2013-01-01

    Carrier envelope phase (CEP) stabilized pulses of intense 800 nm light of 5 fs duration are used to probe the dissociation dynamics of dications of isotopically-substituted water, HOD. HOD$^{2+}$ dissociates into either H$^+$ + OD$^+$ or D$^+$ + OH$^+$. The branching ratio for these two channels is CEP-dependent; the OD$^+$/OH$^+$ ratio (relative to that measured with CEP-unstabilized pulses) varies from 150% to over 300% at different CEP values, opening prospects of isotope-dependent control over molecular bond breakage. The kinetic energy released as HOD$^{2+}$ Coulomb explodes is also CEP-dependent. Formidable theoretical challenges are identified for proper insights into the overall dynamics which involve non-adiabatic field ionization from HOD to HOD$^+$ and, thence, to HOD$^{2+}$ via electron rescattering.

  6. Continuously operated falling film microreactor for selective hydrogenation of carbon-carbon triple bonds

    OpenAIRE

    Rehm, Thomas H.; Berguerand, Charline; Ek, Satu; Zapf, Ralf; Löb, Patrick; Nikoshvili, Linda; Kiwi-Minsker, Lioubov

    2016-01-01

    Despite significant advances in the fabrication and applications of microreactors for production of chemicals, their use for catalytic reactions remains a challenge, especially in fine chemical synthesis where the selectivity towards the desired product is an issue. A falling film microstructured reactor (FFMR) was tested in the selective hydrogenation of 2-butyne-1,4-diol (1) to its olefinic derivative (2). The FFMR plates were coated with Al2O3 or ZnO followed by the deposition of Pd nanopa...

  7. Film/chemistry selection for the earth resources technology satellite /ERTS/ ground data handling system

    Science.gov (United States)

    Shaffer, R. M.

    1973-01-01

    A detailed description is given of the methods of choose the duplication film and chemistry currently used in the NASA-ERTS Ground Data Handling System. The major ERTS photographic duplication goals are given as background information to justify the specifications for the desirable film/chemistry combination. Once these specifications were defined, a quantitative evaluation program was designed and implemented to determine if any recommended combinations could meet the ERTS laboratory specifications. The specifications include tone reproduction, granularity, MTF and cosmetic effects. A complete description of the techniques used to measure the test response variables is given. It is anticipated that similar quantitative techniques could be used on other programs to determine the optimum film/chemistry consistent with the engineering goals of the program.

  8. An evaluation of the performance of chemistry transport models, Part 2: detailed comparison with two selected campaigns

    Directory of Open Access Journals (Sweden)

    D. Brunner

    2004-11-01

    Full Text Available This is the second part of a rigorous model evaluation study involving five global Chemistry-Transport and two Chemistry-Climate Models operated by different groups in Europe. Simulated trace gas fields were interpolated to the exact times and positions of the observations to account for the actual weather conditions and hence for the specific histories of the sampled air masses. In this part of the study we focus on a detailed comparison with two selected campaigns, PEM-Tropics A and SONEX, contrasting the clean environment of the tropical Pacific with the more polluted North Atlantic region. The study highlights the different strengths and weaknesses of the models in accurately simulating key processes in the UT/LS region including stratosphere-troposphere-exchange, rapid convective transport, lightning emissions, radical chemistry and ozone production. Model simulated Radon, which was used as an idealized tracer for continental influence, was occasionally much better correlated with measured CO than simulated CO pointing towards deficiencies in the used biomass burning emission fields. The abundance and variability of HOx radicals is in general well represented in the models as inferred directly from the comparison with measured OH and HO2 and indirectly from the comparison with hydrogen peroxide concentrations. Components of the NOy family such as PAN, HNO3 and NO were found to compare less favorably. Interestingly, models showing good agreement with observations in the case of PEM-Tropics A often failed in the case of SONEX and vice versa. A better description of NOx and NOy emissions, chemistry and sinks is thought to be key to future model improvements with respect to the representation of chemistry in the UT/LS region.

  9. Selecting parameters for the environmental interpretation of peat molecular chemistry - A pyrolysis-GC-MS study

    NARCIS (Netherlands)

    Schellekens, J.F.P.; Buurman, P.; Pontevedra Pombal, X.

    2009-01-01

    A number of samples from a deep peat bog in Tierra del Fuego were analyzed using pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) in order to extract parameters that might be used to interpret the peat chemistry in terms of vegetation change, anaerobic and aerobic decomposition, and fire in

  10. Gender and High School Chemistry: Student Perceptions on Achievement in a Selective Setting

    Science.gov (United States)

    Cousins, Andrew; Mills, Martin

    2015-01-01

    This paper reports on research undertaken in a middle-class Australian school. The focus of the research was on the relationship between gender and students' engagement with high school chemistry. Achievement data from many OECD [Organisation for Economic Co-operation and Development] countries suggest that middle-class girls are achieving equally…

  11. Selectivity on-target of bromodomain chemical probes by structure-guided medicinal chemistry and chemical biology.

    Science.gov (United States)

    Galdeano, Carles; Ciulli, Alessio

    2016-09-01

    Targeting epigenetic proteins is a rapidly growing area for medicinal chemistry and drug discovery. Recent years have seen an explosion of interest in developing small molecules binding to bromodomains, the readers of acetyl-lysine modifications. A plethora of co-crystal structures has motivated focused fragment-based design and optimization programs within both industry and academia. These efforts have yielded several compounds entering the clinic, and many more are increasingly being used as chemical probes to interrogate bromodomain biology. High selectivity of chemical probes is necessary to ensure biological activity is due to an on-target effect. Here, we review the state-of-the-art of bromodomain-targeting compounds, focusing on the structural basis for their on-target selectivity or lack thereof. We also highlight chemical biology approaches to enhance on-target selectivity.

  12. Regulating Biocompatibility of Carbon Spheres via Defined Nanoscale Chemistry and a Careful Selection of Surface Functionalities

    Science.gov (United States)

    Misra, Santosh K.; Chang, Huei-Huei; Mukherjee, Prabuddha; Tiwari, Saumya; Ohoka, Ayako; Pan, Dipanjan

    2015-10-01

    A plethora of nanoarchitectures have been evaluated preclincially for applications in early detection and treatment of diseases at molecular and cellular levels resulted in limited success of their clinical translation. It is important to identify the factors that directly or indirectly affect their use in human. We bring a fundamental understanding of how to adjust the biocompatibility of carbon based spherical nanoparticles (CNPs) through defined chemistry and a vigilant choice of surface functionalities. CNPs of various size are designed by tweaking size (2-250 nm), surface chemistries (positive, or negatively charged), molecular chemistries (linear, dendritic, hyperbranched) and the molecular weight of the coating agents (MW 400-20 kDa). A combination of in vitro assays as tools were performed to determine the critical parameters that may trigger toxicity. Results indicated that hydrodynamic sizes are potentially not a risk factor for triggering cellular and systemic toxicity, whereas the presence of a highly positive surface charge and increasing molecular weight enhance the chance of inducing complement activation. Bare and carboxyl-terminated CNPs did present some toxicity at the cellular level which, however, is not comparable to those caused by positively charged CNPs. Similarly, negatively charged CNPs with hydroxyl and carboxylic functionalities did not cause any hemolysis.

  13. Theoretical chemistry periodicities in chemistry and biology

    CERN Document Server

    Eyring, Henry

    1978-01-01

    Theoretical Chemistry: Periodicities in Chemistry and Biology, Volume 4 covers the aspects of theoretical chemistry. The book discusses the stably rotating patterns of reaction and diffusion; the chemistry of inorganic systems exhibiting nonmonotonic behavior; and population cycles. The text also describes the mathematical modeling of excitable media in neurobiology and chemistry; oscillating enzyme reactions; and oscillatory properties and excitability of the heart cell membrane. Selected topics from the theory of physico-chemical instabilities are also encompassed. Chemists, mechanical engin

  14. Public perception of chemistry

    OpenAIRE

    Stražar, Alenka

    2015-01-01

    The thesis deals with the perception of chemistry among the public, which reflects the stereotypes that people have about chemistry. It presents the existing classification of stereotypes about chemistry and their upgrade. An analysis of movies that reflect the existing perception of chemistry in the public is written. Literature on selected aspects of the application of chemistry in movies is collected and analyzed. A qualification of perception of chemistry in the movies is presented based ...

  15. Two-Dimensional Micro-TLC Phenolic Fingerprints of Selected Mentha sp. on Cyano-Bonded Polar Stationary Phase.

    Science.gov (United States)

    Hawrył, Mirosław A; Niemiec, Małgorzata A; Słomka, Kamil; Waksmundzka-Hajnos, Monika; Szymczak, Grażyna

    2016-01-01

    Micro-thin-layer chromatography in two-dimensional (2D-mTLC) mode in normal- (NP) and reversed-phase (RP) systems by use of cyanopropyl-bonded stationary phases was applied to make fingerprints of 11 species of Mentha genus and two finished pharmaceutical products. Non-aqueous eluents were used in the NP systems. Mixtures of acetonitrile with water and methanol with water were used in the RP chromatographic systems. Optimization of one-dimensional systems was performed by determining RM vs. composition of mobile phase dependencies for standards occurring in various Mentha sp. On the basis of these dependencies, the most selective chromatographic systems for each run were chosen. Then most selective eluents were applied to optimize two-dimensional systems by creating RF in NP systems vs. RF in RP systems correlations. The best two-dimensional systems were chosen on the basis of R(2) values for RF vs. RF correlations (the lowest values of R(2) coefficients). The 2D-mTLC optimized systems were applied to separate phenolic compounds and make fingerprints of the examined plant materials.

  16. Two-Dimensional Micro-TLC Phenolic Fingerprints of Selected Mentha sp. on Cyano-Bonded Polar Stationary Phase.

    Science.gov (United States)

    Hawrył, Mirosław A; Niemiec, Małgorzata A; Słomka, Kamil; Waksmundzka-Hajnos, Monika; Szymczak, Grażyna

    2016-01-01

    Micro-thin-layer chromatography in two-dimensional (2D-mTLC) mode in normal- (NP) and reversed-phase (RP) systems by use of cyanopropyl-bonded stationary phases was applied to make fingerprints of 11 species of Mentha genus and two finished pharmaceutical products. Non-aqueous eluents were used in the NP systems. Mixtures of acetonitrile with water and methanol with water were used in the RP chromatographic systems. Optimization of one-dimensional systems was performed by determining RM vs. composition of mobile phase dependencies for standards occurring in various Mentha sp. On the basis of these dependencies, the most selective chromatographic systems for each run were chosen. Then most selective eluents were applied to optimize two-dimensional systems by creating RF in NP systems vs. RF in RP systems correlations. The best two-dimensional systems were chosen on the basis of R(2) values for RF vs. RF correlations (the lowest values of R(2) coefficients). The 2D-mTLC optimized systems were applied to separate phenolic compounds and make fingerprints of the examined plant materials. PMID:26673190

  17. Design of Highly Selective Platinum Nanoparticle Catalysts for the Aerobic Oxidation of KA-Oil using Continuous-Flow Chemistry.

    Science.gov (United States)

    Gill, Arran M; Hinde, Christopher S; Leary, Rowan K; Potter, Matthew E; Jouve, Andrea; Wells, Peter P; Midgley, Paul A; Thomas, John M; Raja, Robert

    2016-03-01

    Highly active and selective aerobic oxidation of KA-oil to cyclohexanone (precursor for adipic acid and ɛ-caprolactam) has been achieved in high yields using continuous-flow chemistry by utilizing uncapped noble-metal (Au, Pt & Pd) nanoparticle catalysts. These are prepared using a one-step in situ methodology, within three-dimensional porous molecular architectures, to afford robust heterogeneous catalysts. Detailed spectroscopic characterization of the nature of the active sites at the molecular level, coupled with aberration-corrected scanning transmission electron microscopy, reveals that the synthetic methodology and associated activation procedures play a vital role in regulating the morphology, shape and size of the metal nanoparticles. These active centers have a profound influence on the activation of molecular oxygen for selective catalytic oxidations.

  18. Gas-phase chemistry of Sc(CH{sub 3}){sub 2}{sup +} with alkenes: Activation of allylic C-H bonds by a d{sup 0} system and the migratory insertion of C=C bonds into Sc{sup +}-CH{sub 3} bonds

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yongqing; Hill, Y.D.; Freiser, B.S. [Purdue Univ., West Lafayette, IN (United States)] [and others

    1992-11-04

    The gas-phase chemistry of Sc(CH{sub 3}){sub 2}{sup +} with alkenes was studied by Fourier transform mass spectrometry. The metal center on Sc(CH{sub 3}){sub 2}{sup +} is d{sup 0}, providing an opportunity to study alternative mechanisms of C-C or C-H activation other than the most common one involving oxidative addition. The elimination of H{sub 2} is observed in the reaction of Sc(CH{sub 3}){sub 2}{sup +} with ethylene, and the product ScC{sub 4}H{sub 8}{sup +} and ScC{sub 6}H{sub 10}{sup +} ions have a metal(methyl)(allyl) and metal-bisallyl structure, respectively, consistent with a proposed reaction mechanism involving the consecutive migratory insertion of ethylenes into the scandium-methyl bonds. In addition, theoretical calculations indicate that the metal(methyl)(allyl) structure is between 10 and 20 kcal/mol more stable than the metal(1-butene) isomer. Sc(CH{sub 3}){sub 2}{sup +} reacts with propene to form predominantly ScC{sub 4}H{sub 8}{sup +} by loss of CH{sub 4}, with minor amounts of ScC{sub 3}H{sub 4}{sup +} and ScC{sub 4}H{sub 6}{sup +} also observed. ScC{sub 4}H{sub 6}{sup +} is formed as either the exclusive or the predominant product ion in the reactions of Sc(CH{sub 3}){sub 2}{sup +} with butenes. Sc(CH{sub 3}){sub 2} reacts with cyclopentene to form predominantly ScC{sub 6}H{sub 8}{sup +} by losing CH{sub 4} and H{sub 2}. Isotope labeling studies with Sc(CD{sub 3}){sub 2}{sup +} and other structure studies indicate that all of the alkenes studied, with the exception of ethylene, react with Sc(CH{sub 3}){sub 2}{sup +} via a multicentered {sigma}-bond metathesis mechanism to activate allylic C-H bonds. Finally, the dehydrogenation reactions of Sc{sup +} with n-butane and neopentane were revisited, and a new mechanism is proposed for such chemistry in light of the new results from this study. 34 refs., 5 figs., 2 tabs.

  19. Highly efficient and selective enrichment of peptide subsets combining fluorous chemistry with reversed-phase chromatography

    OpenAIRE

    Ying, Wantao; Perlman, David H.; Li, Lei(Beijing Institute of Petrochemical Technology, Beijing, 102617, People's Republic of China); Théberge, Roger; Costello, Catherine E; McComb, Mark E.

    2009-01-01

    The selective capture of target peptides poses a great challenge to modern chemists and biologists, especially when enriching them from proteome samples possessing extremes in concentration dynamic range and sequence diversity. While approaches based on traditional techniques such as biotin-avidin pairing offer versatile tools to design strategies for selective enrichment, problems are still encountered due to sample loss or poor selectivity of enrichment. Here we show that the recently intro...

  20. Chemistry principles for thermoplastic polymer binder formula selection for powder injection molding

    Institute of Scientific and Technical Information of China (English)

    梁叔全; 唐艳; 黄伯云; 李少强

    2004-01-01

    The polymer binder selection is one of the very important aspects for the powder injection molding.However, even nowadays the binder selection is still mainly performed by try and error method. Six commercial or intensive studied binder formulas were analyzed according to state diagram and chemical characteristics of ingredients in each binder formula. In addition, the interactions between the binder components and additives were also taken into account. Based on the analysis, the optimum binder formula was selected and some selection criterions were put forward for the binder and additives.

  1. Selective Gas-Phase Oxidation and Localization of Alkylated Cysteine Residues in Polypeptide Ions via Ion/Ion Chemistry.

    Science.gov (United States)

    Pilo, Alice L; Zhao, Feifei; McLuckey, Scott A

    2016-09-01

    The thiol group in cysteine residues is susceptible to several post-translational modifications (PTMs), including prenylation, nitrosylation, palmitoylation, and the formation of disulfide bonds. Additionally, cysteine residues involved in disulfide bonds are commonly reduced and alkylated prior to mass spectrometric analysis. Several of these cysteine modifications, specifically S-alkyl modifications, are susceptible to gas-phase oxidation via selective ion/ion reactions with periodate anions. Multiply protonated peptides containing modified cysteine residues undergo complex formation upon ion/ion reaction with periodate anions. Activation of the ion/ion complexes results in oxygen transfer from the reagent to the modified sulfur residue to create a sulfoxide functionality. Further activation of the sulfoxide derivative yields abundant losses of the modification with the oxidized sulfur as a sulfenic acid (namely, XSOH) to generate a dehydroalanine residue. This loss immediately indicates the presence of an S-alkyl cysteine residue, and the mass of the loss can be used to easily deduce the type of modification. An additional step of activation can be used to localize the modification to a specific residue within the peptide. Selective cleavage to create c- and z-ions N-terminal to the dehydroalanine residue is often noted. As these types of ions are not typically observed upon collision-induced dissociation (CID), they can be used to immediately indicate where in the peptide the PTM was originally located.

  2. Selective Gas-Phase Oxidation and Localization of Alkylated Cysteine Residues in Polypeptide Ions via Ion/Ion Chemistry.

    Science.gov (United States)

    Pilo, Alice L; Zhao, Feifei; McLuckey, Scott A

    2016-09-01

    The thiol group in cysteine residues is susceptible to several post-translational modifications (PTMs), including prenylation, nitrosylation, palmitoylation, and the formation of disulfide bonds. Additionally, cysteine residues involved in disulfide bonds are commonly reduced and alkylated prior to mass spectrometric analysis. Several of these cysteine modifications, specifically S-alkyl modifications, are susceptible to gas-phase oxidation via selective ion/ion reactions with periodate anions. Multiply protonated peptides containing modified cysteine residues undergo complex formation upon ion/ion reaction with periodate anions. Activation of the ion/ion complexes results in oxygen transfer from the reagent to the modified sulfur residue to create a sulfoxide functionality. Further activation of the sulfoxide derivative yields abundant losses of the modification with the oxidized sulfur as a sulfenic acid (namely, XSOH) to generate a dehydroalanine residue. This loss immediately indicates the presence of an S-alkyl cysteine residue, and the mass of the loss can be used to easily deduce the type of modification. An additional step of activation can be used to localize the modification to a specific residue within the peptide. Selective cleavage to create c- and z-ions N-terminal to the dehydroalanine residue is often noted. As these types of ions are not typically observed upon collision-induced dissociation (CID), they can be used to immediately indicate where in the peptide the PTM was originally located. PMID:27476698

  3. Selected constants oxydo-reduction potentials tables of constants and numerical data affiliated to the International Union of Pure and Applied Chemistry, v.8

    CERN Document Server

    Charlot, G

    1958-01-01

    Selected Constants: Oxydo-Reduction Potentials contains Tables of the most probable value of the normal oxidation-reduction potential, or of the formal or apparent potential, of a given oxidation-reduction system. This book is prepared under the sponsorship of the Commission on Electrochemical Data of the Section of Analytical Chemistry of the International Union of Pure and Applied Chemistry. It is included in a general program of the Section of Analytical Chemistry. Entry items are classified in alphabetical order. This book will be of value to specialized and non-specialized chemists, teach

  4. Solution chemistry of a water-soluble eta2-H2 ruthenium complex: evidence for coordinated H2 acting as a hydrogen bond donor.

    Science.gov (United States)

    Szymczak, Nathaniel K; Zakharov, Lev N; Tyler, David R

    2006-12-13

    The ability of an eta2-H2 ligand to participate in intermolecular hydrogen bonding in solution has long been an unresolved issue. Such species are proposed to be key intermediates in numerous important reactions such as the proton-transfer pathway of H2 production by hydrogenase enzymes. We present the synthesis of several new water-soluble ruthenium coordination complexes including an eta2-H2 complex that is surprisingly inert to substitution by water. The existence of dihydrogen hydrogen bonding (DHHB) was experimentally probed by monitoring the chemical shift of H-bonded Ru-(H2) complexes using NMR spectroscopy, by UV-visible spectroscopy, and by monitoring the rotational dynamics of a hydrogen-bonding probe molecule. The results provide strong evidence that coordinated H2 can indeed participate in intermolecular hydrogen bonding to bulk solvent and other H-bond acceptors. PMID:17147394

  5. A rod-packing microporous hydrogen-bonded organic framework for highly selective separation of C2H2/CO2at room temperature

    KAUST Repository

    Li, Peng

    2014-11-13

    Self-assembly of a trigonal building subunit with diaminotriazines (DAT) functional groups leads to a unique rod-packing 3D microporous hydrogen-bonded organic framework (HOF-3). This material shows permanent porosity and demonstrates highly selective separation of C2H2/CO2 at ambient temperature and pressure.

  6. Selective androgen receptor modulators in drug discovery: medicinal chemistry and therapeutic potential.

    Science.gov (United States)

    Cadilla, Rodolfo; Turnbull, Philip

    2006-01-01

    Modulation of the androgen receptor has the potential to be an effective treatment for hypogonadism, andropause, and associated conditions such as sarcopenia, osteoporosis, benign prostatic hyperplasia, and sexual dysfunction. Side effects associated with classical anabolic steroid treatments have driven the quest for drugs that demonstrate improved therapeutic profiles. Novel, non-steroidal compounds that show tissue selective activity and improved pharmacokinetic properties have been developed. This review provides an overview of current advances in the development of selective androgen receptor modulators (SARMs).

  7. Comparison of the single channel and multichannel (multivariate) concepts of selectivity in analytical chemistry.

    Science.gov (United States)

    Dorkó, Zsanett; Verbić, Tatjana; Horvai, George

    2015-07-01

    Different measures of selectivity are in use for single channel and multichannel linear analytical measurements, respectively. It is important to understand that these two measures express related but still distinctly different features of the respective measurements. These relationships are clarified by introducing new arguments. The most widely used selectivity measure of multichannel linear methods (which is based on the net analyte signal, NAS, concept) expresses the sensitivity to random errors of a determination where all bias from interferents is computationally eliminated using pure component spectra. The conventional selectivity measure of single channel linear measurements, on the other hand, helps to estimate the bias caused by an interferent in a biased measurement. In single channel methods expert knowledge about the samples is used to limit the possible range of interferent concentrations. The same kind of expert knowledge allows improved (lower mean squared error, MSE) analyte determinations also in "classical" multichannel measurements if those are intractable due to perfect collinearity or to high noise inflation. To achieve this goal bias variance tradeoff is employed, hence there remains some bias in the results and therefore the concept of single channel selectivity can be extended in a natural way to multichannel measurements. This extended definition and the resulting selectivity measure can also be applied to the so-called inverse multivariate methods like partial least squares regression (PLSR), principal component regression (PCR) and ridge regression (RR).

  8. Controlling orbital-selective Kondo effects in a single molecule through coordination chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Tsukahara, Noriyuki; Kawai, Maki; Takagi, Noriaki, E-mail: n-takagi@k.u-tokyo.ac.jp [Department of Advanced Materials Science, The University of Tokyo, 5-1-5 Kashiwanoha, Kashiwa, Chiba 277-8561 (Japan); Minamitani, Emi; Kim, Yousoo [RIKEN, 2-1 Hirosawa, Saitama 351-0198 (Japan)

    2014-08-07

    Iron(II) phthalocyanine (FePc) molecule causes novel Kondo effects derived from the unique electronic structure of multi-spins and multi-orbitals when attached to Au(111). Two unpaired electrons in the d{sub z}{sup 2} and the degenerate dπ orbitals are screened stepwise, resulting in spin and spin+orbital Kondo effects, respectively. We investigated the impact on the Kondo effects of the coordination of CO and NO molecules to the Fe{sup 2+} ion as chemical stimuli by using scanning tunneling microscopy (STM) and density functional theory calculations. The impacts of the two diatomic molecules are different from each other as a result of the different electronic configurations. The coordination of CO converts the spin state from triplet to singlet, and then the Kondo effects completely disappear. In contrast, an unpaired electron survives in the molecular orbital composed of Fe d{sub z}{sup 2} and NO 5σ and 2π* orbitals for the coordination of NO, causing a sharp Kondo resonance. The isotropic magnetic response of the peak indicates the origin is the spin Kondo effect. The diatomic molecules attached to the Fe{sup 2+} ion were easily detached by applying a pulsed voltage at the STM junction. These results demonstrate that the single molecule chemistry enables us to switch and control the spin and the many-body quantum states reversibly.

  9. Effects of fenbendazole administration on hematology, clinical chemistries and selected hormones in the white Pekin duck.

    Science.gov (United States)

    Pedersoli, W M; Spano, J S; Krista, L M; Whitesides, J F; Ravis, W R; Kemppainen, R J; Young, D W

    1989-06-01

    The effects of single i.v. and p.o. doses (5 mg/kg) of fenbendazole, were evaluated on thyroxine, tri-iodothyronine, corticosterone, hematology, clinical chemistries, and serum proteins in 10 white Pekin ducks. Fenbendazole was administered i.v. (n = 5) as a 3% dimethyl sulfoxide solution and p.o. (n = 5) as a 10% commercial suspension. Serum enzyme concentrations, total protein and protein fractions, glucose, cholesterol, uric acid, sodium, and potassium were unchanged from baseline values. Serum triglycerides decreased consistently in the i.v.-treated group but remained unchanged in the p.o.-treated group. Serum chloride was consistently elevated above baseline values for both i.v.- and p.o.-treated ducks, while inorganic phosphate was consistently decreased only in the i.v.-treated group. Hemoglobin and hematocrit values generally were below baseline values. Leukocyte values varied considerably and were not significantly different from baseline values. Serum thyroxine and tri-iodothyronine values in both the i.v.- and p.o.-treated groups were not changed significantly from baseline values. Serum corticosterone values were not changed in the i.v.-treated groups but they were decreased at various times in the p.o.-treated group. Although there were some sporadic significant changes in the parameters measured versus baseline values all values remained within the physiologic limits for ducks. The safety of fenbendazole has been previously demonstrated for several species.

  10. Chemistry of Secondary Polyphenols Produced during Processing of Tea and Selected Foods

    Directory of Open Access Journals (Sweden)

    Takashi Tanaka

    2009-12-01

    Full Text Available This review will discuss recent progress in the chemistry of secondary polyphenols produced during food processing. The production mechanism of the secondary polyphenols in black tea, whisky, cinnamon, and persimmon fruits will be introduced. In the process of black tea production, tea leaf catechins are enzymatically oxidized to yield a complex mixture of oxidation products, including theaflavins and thearubigins. Despite the importance of the beverage, most of the chemical constituents have not yet been confirmed due to the complexity of the mixture. However, the reaction mechanisms at the initial stages of catechin oxidation are explained by simple quinone–phenol coupling reactions. In vitro model experiments indicated the presence of interesting regio- and stereoselective reactions. Recent results on the reaction mechanisms will be introduced. During the aging of whisky in oak wood barrels, ellagitannins originating from oak wood are oxidized and react with ethanol to give characteristic secondary ellagitannins. The major part of the cinnamon procyanidins is polymerized by copolymerization with cinnamaldehyde. In addition, anthocyanidin structural units are generated in the polymer molecules by oxidation which accounts for the reddish coloration of the cinnamon extract. This reaction is related to the insolubilization of proanthocyanidins in persimmon fruits by condensation with acetaldehyde. In addition to oxidation, the reaction of polyphenols with aldehydes may be important in food processing.

  11. Directing Group in Decarboxylative Cross-Coupling: Copper-Catalyzed Site-Selective C-N Bond Formation from Nonactivated Aliphatic Carboxylic Acids.

    Science.gov (United States)

    Liu, Zhao-Jing; Lu, Xi; Wang, Guan; Li, Lei; Jiang, Wei-Tao; Wang, Yu-Dong; Xiao, Bin; Fu, Yao

    2016-08-01

    Copper-catalyzed directed decarboxylative amination of nonactivated aliphatic carboxylic acids is described. This intramolecular C-N bond formation reaction provides efficient access to the synthesis of pyrrolidine and piperidine derivatives as well as the modification of complex natural products. Moreover, this reaction presents excellent site-selectivity in the C-N bond formation step through the use of directing group. Our work can be considered as a big step toward controllable radical decarboxylative carbon-heteroatom cross-coupling. PMID:27439145

  12. A Selective Study Approach to Organic Chemistry for Health Science Majors

    Science.gov (United States)

    Mueller, William J.

    1974-01-01

    Bulk of the course deals with reactions of the carbonyl group. Topic selection and ordering were based on the need to prepare the students for a succeeding biochemistry course, and the lecture-test method of instruction was adopted because of efficiency demands of teaching. (GS)

  13. Effect of Electronic Factor in Ru-phosphine-diamine Complexes on Selective Hydrogenation of C=C and C-O Bonds

    Institute of Scientific and Technical Information of China (English)

    ZHANG,Yu; Yu,Xiaojun; YU,Changbin; XIA,Yuqing; LI,Ruixiang; CHEN,Hua; LI,Xianjun

    2009-01-01

    A series of ruthenium complexes bearing different phosphines and diamines were synthesized and their compo-nents and structures were characterized by NMR spectra and elemental analyses. The catalytic properties of these complexes for the hydrogenation of benzylideneacetone and the mixture of acetophenone and styrene were investi-gated. The results showed that the basicity increase of phosphine or diamine dramatically facilitates the hydrogena-tion activity and selectivity to C=O double bond. On the contrary, the basicity decrease of phosphine or diamine not only slows down the catalytic activity, but also significantly suppresses the hydrogenation selectivity to C=O double bond. Based on the effect of electron factors of these complexes on the hydrogenation activity and selectiv-ity of benzylideneacetone and the mixture of styrene and acetophenone, the activation mechanism of dihydrogen in ruthenium-phosphine-diamine system was proposed.

  14. Response of lake chemistry to atmospheric deposition and climate in selected Class I wilderness areas in the western United States, 1993-2009

    Science.gov (United States)

    Mast, M. Alisa

    2011-01-01

    The U.S. Geological Survey, in cooperation with the U.S. Department of Agriculture Forest Service, Air Resource Management, conducted a study to evaluate long-term trends in lake-water chemistry for 64 high-elevation lakes in selected Class I wilderness areas in Colorado, Idaho, Utah, and Wyoming during 1993 to 2009. Understanding how and why lake chemistry is changing in mountain areas is essential for effectively managing and protecting high-elevation aquatic ecosystems. Trends in emissions, atmospheric deposition, and climate variables (air temperature and precipitation amount) were evaluated over a similar period of record. A main objective of the study was to determine if changes in atmospheric deposition of contaminants in the Rocky Mountain region have resulted in measurable changes in the chemistry of high-elevation lakes. A second objective was to investigate linkages between lake chemistry and air temperature and precipitation to improve understanding of the sensitivity of mountain lakes to climate variability.

  15. The unique chemistry of Eastern Mediterranean water masses selects for distinct microbial communities by depth.

    Directory of Open Access Journals (Sweden)

    Stephen M Techtmann

    Full Text Available The waters of the Eastern Mediterranean are characterized by unique physical and chemical properties within separate water masses occupying different depths. Distinct water masses are present throughout the oceans, which drive thermohaline circulation. These water masses may contain specific microbial assemblages. The goal of this study was to examine the effect of physical and geological phenomena on the microbial community of the Eastern Mediterranean water column. Chemical measurements were combined with phospholipid fatty acid (PLFA analysis and high-throughput 16S rRNA sequencing to characterize the microbial community in the water column at five sites. We demonstrate that the chemistry and microbial community of the water column were stratified into three distinct water masses. The salinity and nutrient concentrations vary between these water masses. Nutrient concentrations increased with depth, and salinity was highest in the intermediate water mass. Our PLFA analysis indicated different lipid classes were abundant in each water mass, suggesting that distinct groups of microbes inhabit these water masses. 16S rRNA gene sequencing confirmed the presence of distinct microbial communities in each water mass. Taxa involved in autotrophic nitrogen cycling were enriched in the intermediate water mass suggesting that microbes in this water mass may be important to the nitrogen cycle of the Eastern Mediterranean. The Eastern Mediterranean also contains numerous active hydrocarbon seeps. We sampled above the North Alex Mud Volcano, in order to test the effect of these geological features on the microbial community in the adjacent water column. The community in the waters overlaying the mud volcano was distinct from other communities collected at similar depths and was enriched in known hydrocarbon degrading taxa. Our results demonstrate that physical phenomena such stratification as well as geological phenomena such as mud volcanoes strongly

  16. The geology, botany and chemistry of selected peat-forming environments from temperate and tropical latitudes

    Energy Technology Data Exchange (ETDEWEB)

    Cameron, C.C.; Esterle, J.S.; Palmer, C.A. (US Geological Survey, Reston, VA (USA))

    1989-06-01

    Several peat forming deposits typical of temperate and tropical latitudes that were selected as representing principles of stratigraphic development are described. Their organic and inorganic contents are related to their geomorphology. The general nature of commercial-quality peat and its formation are briefly outlined. The stratigraphy of each peat deposit reflects a succession of peat-forming environments that can be identified with their modern-equivalent bogs, swamps and marshes. Types of peat in each deposit reflect the kind of peat-forming vegetation and degree of decomposition. Models and processes of peat accumulation are described to provide a frame of reference for understanding the geomorphology of the selected deposits. 64 refs., 15 figs., 5 tabs.

  17. Modifying the chemistry of graphene with substrate selection: A study of gold nanoparticle formation

    International Nuclear Information System (INIS)

    Graphene and metal nanoparticle composites are a promising class of materials with unique electronic, optical, and chemical properties. In this work, graphene is used as a reducing surface to grow gold nanoparticles out of solution-based metal precursors. The nanoparticle formation is found to strongly depend upon the graphene substrate selection. The studied substrates include diamond, p-type silicon, aluminum oxide, lithium niobate, and copper. Our results indicate that the chemical properties of graphene depend upon this selection. For example, for the same reaction times and concentration, the reduction of gold chloride to gold nanoparticles on graphene/lithium niobate results in 3% nanoparticle coverage compared to 20% coverage on graphene/silicon and 60% on graphene/copper. On insulators, nanoparticles preferentially form on folds and edges. Energy dispersive X-ray analysis is used to confirm the nanoparticle elemental makeup

  18. Modifying the chemistry of graphene with substrate selection: A study of gold nanoparticle formation

    Energy Technology Data Exchange (ETDEWEB)

    Zaniewski, Anna M.; Trimble, Christie J.; Nemanich, Robert J. [Department of Physics, Arizona State University, Tempe, Arizona 85281 (United States)

    2015-03-23

    Graphene and metal nanoparticle composites are a promising class of materials with unique electronic, optical, and chemical properties. In this work, graphene is used as a reducing surface to grow gold nanoparticles out of solution-based metal precursors. The nanoparticle formation is found to strongly depend upon the graphene substrate selection. The studied substrates include diamond, p-type silicon, aluminum oxide, lithium niobate, and copper. Our results indicate that the chemical properties of graphene depend upon this selection. For example, for the same reaction times and concentration, the reduction of gold chloride to gold nanoparticles on graphene/lithium niobate results in 3% nanoparticle coverage compared to 20% coverage on graphene/silicon and 60% on graphene/copper. On insulators, nanoparticles preferentially form on folds and edges. Energy dispersive X-ray analysis is used to confirm the nanoparticle elemental makeup.

  19. Anion Receptor Design: Exploiting Outer-Sphere Coordination Chemistry To Obtain High Selectivity for Chloridometalates over Chloride.

    Science.gov (United States)

    Carson, Innis; MacRuary, Kirstian J; Doidge, Euan D; Ellis, Ross J; Grant, Richard A; Gordon, Ross J; Love, Jason B; Morrison, Carole A; Nichol, Gary S; Tasker, Peter A; Wilson, A Matthew

    2015-09-01

    High anion selectivity for PtCl6(2-) over Cl(-) is shown by a series of amidoamines, R(1)R(2)NCOCH2CH2NR(3)R(4) (L1 with R(1) = R(4) = benzyl and R(2) = R(3) = phenyl and L3 with R(1) = H, R(2) = 2-ethylhexyl, R(3) = phenyl and R(4) = methyl), and amidoethers, R(1)R(2)NCOCH2CH2OR(3) (L5 with R(1) = H, R(2) = 2-ethylhexyl and R(3) = phenyl), which provide receptor sites which extract PtCl6(2-) preferentially over Cl(-) in extractions from 6 M HCl solutions. The amidoether receptor L5 was found to be a much weaker extractant for PtCl6(2-) than its amidoamine analogues. Density functional theory calculations indicate that this is due to the difficulty in protonating the amidoether to generate a cationic receptor, LH(+), rather than the latter showing weaker binding to PtCl6(2-). The most stable forms of the receptors, LH(+), contain a tautomer in which the added proton forms an intramolecular hydrogen bond to the amide oxygen atom to give a six-membered proton chelate. Dispersion-corrected DFT calculations appear to suggest a switch in ligand conformation for the amidoamine ligands to an open tautomer state in the complex, such that the cationic N-H or O-H groups are also readily available to form hydrogen bonds to the PtCl6(2-) ion, in addition to the array of polarized C-H bonds. The predicted difference in energies between the proton chelate and nonchelated tautomer states for L1 is small, however, and the former is found in the X-ray crystal structure of the assembly [(L1H)2PtCl6]. The DFT calculations and the X-ray structure indicate that all LH(+) receptors present an array of polarized C-H groups to the large, charge diffuse PtCl6(2-) anion resulting in high selectivity of extraction of PtCl6(2-) over the large excess of chloride.

  20. Nobel Prize in Chemistry

    Science.gov (United States)

    2000-01-01

    The Royal Swedish Academy has awarded the 1999 Nobel Prize in Chemistry to Ahmed H. Zewail (California Institute of Technology, Pasadena, CA) "for his studies of the transition states of chemical reactions using femtosecond spectroscopy". Zewail's work has taken the study of the rates and mechanisms of chemical reactions to the ultimate degree of detail - the time scale of bond making and bond breaking.

  1. Novel trends in electrocatalysis: Extended Brewer hypo-hyper-d-interionic bonding theory and selective interactive grafting of composite bifunctional electrocatalysts for simultaneous anodic hydrogen

    Directory of Open Access Journals (Sweden)

    Neophytides S.G.

    2003-01-01

    Full Text Available Novel Trends in Electrocatalysis: Extended Brewer Hypo-Hyper-d-lnterionic Bonding Theory and Selective Interactive Grafting of Composite Bifunctional Electrocatalysts for Simultaneous Anodic Hydrogen and CO OxidationThe Extended Brewer Interactive Interionic Bonding Theory (EBIIBT has been developed to show the equivalence of interatomic and interionic bonding features, and for their mutual combinations, as well as its effect upon electrocatalytic properties for the hydrogen electrode reactions (HELR. The equivalence of interionic hypo-hyper-d-interelectronic interaction in both metallic and any other ionic state and its effect upon electrocatalytic properties for hydrogen electrode reactions (HELR has been proved and inferred. TG (Thermal Gravimetry analysis of TPR (Temperature Programmed Reduction of mixed hypc-hyper-d-electronic oxides of transition elements was broadly employed to prove the EBIIBT effect as reflected in dramatically decreased individual temperatures of their mutual reduction into intermetallic phases. The same interionic Brewer (and/or intermetallic bonding effect has been confirmed both by UPD of hyper-d-upon hypo-d-electronic substrates and vice versa, and by the shift of bonding peaks in XPS analysis.

  2. Non-selective chemical sensors in analytical chemistry: from ''electronic nose'' to ''electronic tongue''

    International Nuclear Information System (INIS)

    Development, recent historical background and analytical applications of promising sensor instruments based on sensor arrays with data processing by pattern recognition methods have been described. Attention is paid to the ''electronic tongue'' based on an array of original non-specific (non-selective) potentiometric chemical sensors. Application results for integral qualitative analysis of beverages and for quantitative analysis of biological liquids and solutions, containing heavy metals are reported. Discriminating abilities and precision obtained allow to consider ''electronic tongue'' as a perspective analytical tool. (orig.)

  3. Synthesis of 1,2,4-Triazoles via Oxidative Heterocyclization: Selective C-N Bond Over C-S Bond Formation.

    Science.gov (United States)

    Gogoi, Anupal; Guin, Srimanta; Rajamanickam, Suresh; Rout, Saroj Kumar; Patel, Bhisma K

    2015-09-18

    The higher propensity of C-N over C-S bond forming ability was demonstrated, through formal C-H functionalization during the construction of 4,5-disubstituted 1,2,4-triazole-3-thiones from arylidenearylthiosemicarbazides catalyzed by Cu(II). However, steric factors imparted by the o-disubstituted substrates tend to change the reaction path giving thiodiazole as the major or an exclusive product. Upon prolonging the reaction time, the in situ generated thiones are transformed to 4,5-disubstituted 1,2,4-triazoles via a desulfurization process. Two classes of heterocycles viz. 4,5-disubstituted 1,2,4-triazole-3-thiones and 4,5-disubstituted 1,2,4-triazoles can be synthesized from arylidenearylthiosemicarbazides by simply adjusting the reaction time. Desulfurization of 1,2,4-triazole-3-thiones is assisted by thiophilic Cu to provide 1,2,4-triazoles with concomitant formation of CuS and polynuclear sulfur anions as confirmed from scanning electron microscope and energy dispersive X-ray spectroscopy measurements. A one-pot synthesis of an antimicrobial compound has been successfully achieved following this strategy. PMID:26332253

  4. Site-selective protein-modification chemistry for basic biology and drug development

    Science.gov (United States)

    Krall, Nikolaus; da Cruz, Filipa P.; Boutureira, Omar; Bernardes, Gonçalo J. L.

    2016-02-01

    Nature has produced intricate machinery to covalently diversify the structure of proteins after their synthesis in the ribosome. In an attempt to mimic nature, chemists have developed a large set of reactions that enable post-expression modification of proteins at pre-determined sites. These reactions are now used to selectively install particular modifications on proteins for many biological and therapeutic applications. For example, they provide an opportunity to install post-translational modifications on proteins to determine their exact biological roles. Labelling of proteins in live cells with fluorescent dyes allows protein uptake and intracellular trafficking to be tracked and also enables physiological parameters to be measured optically. Through the conjugation of potent cytotoxicants to antibodies, novel anti-cancer drugs with improved efficacy and reduced side effects may be obtained. In this Perspective, we highlight the most exciting current and future applications of chemical site-selective protein modification and consider which hurdles still need to be overcome for more widespread use.

  5. [Highly selective analysis of biogenic-related compounds utilizing fluorous chemistry].

    Science.gov (United States)

    Hayama, Tadashi

    2015-01-01

    Perfluoroalkyl-containing compounds are highly fluorous, meaning that they have a remarkable affinity for one another and effectively exclude non-fluorous species. Utilizing this unique property, we have developed a fluorous derivatization with a liquid chromatographic analysis method for highly selective analysis of target analytes. Although most previous methods focused on extremely sensitive detection-oriented derivatization, the fluorous derivatization method involves highly specific separation for analytes. This method includes perfluoroalkylation of analytes with a fluorous reagent, and separation of the derivatives using a perfluoroalkyl-modified stationary phase LC column. The derivatives can be selectively retained on the fluorous-phase LC column, whereas the non-fluorous derivatives are poorly retained under the same separation conditions. The combination of this method with LC-tandem mass spectrometry (MS/MS) is very useful for complex biological sample analysis, because matrix-induced suppression effects, which are a common problem in LC-MS/MS analysis arising from components of a biological endogenous matrix, have not been observed. We have successfully applied this method to precise and accurate LC-MS/MS analysis of some biogenic compounds, such as sialic acids and biogenic amines, in complex biological samples. PMID:25747214

  6. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance. Final Report

    International Nuclear Information System (INIS)

    This project focused on identifying selective binding agents for the removal of negative ions that hamper vitrification efforts. The project was led by Professor Kristin Bowman-James at the University of Kansas (KU) and consisted of a collaborative effort between the KU group, the group of Professor Jonathan Sessler at the University of Texas Austin (UT), and Dr. Bruce Moyer at Oak Ridge National Laboratory (ORNL). Research efforts during this funding period have focused on a particularly difficult target species, sulfate ion, which is highly insoluble in borosilicate glass. The project is unique in that it combines the synthetic expertise of the Bowman-James and Sessler groups with the analytical/extraction expertise of the Moyer group at ORNL, with a synergy that can bridge disciplines. Sulfate ion is a relatively small ionic species that, because of its solubility characteristics as well as its caustic nature, are a hindrance to the vitrification process. Not only is it relatively insoluble in the medium that has been chosen to store the wastes, but it also has the potential for accelerating the corrosion of the furnaces used to vitrify the borosilicate in a liquid to allow for waste incorporation. The goal of the Bowman-James group has been to design sequestering agents for sulfate that are selective for that ion over nitrate, for example, to allow for a liquid-liquid extraction step that can remove most of the sulfate prior to vitrification. The collaborative design efforts between the Bowman-James and Sessler groups helped to accelerate progress in the design process. In particular the Bowman-James group has been probing the influence of dimensionality and charge on sulfate binding, i.e., progressing from circular to spherical extractants, while at the same time adding positive charges to the agents so that when sulfate is bound, the resulting species is neutral. Not only does this project serve to benefit the remediation process, but it also provides an

  7. Surface chemistry on small ruthenium nanoparticles: evidence for site selective reactions and influence of ligands.

    Science.gov (United States)

    Novio, Fernando; Monahan, Daniele; Coppel, Yannick; Antorrena, Guillermo; Lecante, Pierre; Philippot, Karine; Chaudret, Bruno

    2014-01-27

    The reactivity of two classes of ruthenium nanoparticles (Ru NPs) of small size, either sterically stabilized by a polymer (polyvinylpyrrolidone, PVP) or electronically stabilized by a ligand (bisdiphenylphosphinobutane, dppb) was tested towards standard reactions, namely CO oxidation, CO2 reduction and styrene hydrogenation. The aim of the work was to identify the sites of reactivity on the nanoparticles and to study how the presence of ancillary ligands can influence the course of these catalytic reactions by using NMR and IR spectroscopies. It was found that CO oxidation proceeds at room temperature (RT) on Ru NPs but that the system deactivates rapidly in the absence of ligands because of the formation of RuO2. In the presence of ligands, the reaction involves exclusively the bridging CO groups and no bulk oxidation is observed at RT under catalytic conditions. The reverse reaction, CO2 reduction, is achieved at 120 °C in the presence of H2 and leads to CO, which coordinates exclusively in a bridging mode, hence evidencing the competition between hydrides and CO for coordination on Ru NPs. The effect of ligands localized on the surface is also evidenced in catalytic reactions. Thus, styrene is slowly hydrogenated at RT by the two systems Ru/PVP and Ru/dppb, first into ethylbenzene and then into ethylcyclohexane. Selectively poisoning the nanoparticles with bridging CO groups leads to catalysts that are only able to reduce the vinyl group of styrene whereas a full poisoning with both terminal and bridging CO groups leads to inactive catalysts. These results are interpreted in terms of location of the ligands on the particles surface, and evidence site selectivity for both CO oxidation and arene hydrogenation. PMID:24458912

  8. Effect of nonthermal plasma treatment on surface chemistry of commercially-pure titanium and shear bond strength to autopolymerizing acrylic resin.

    Science.gov (United States)

    Vechiato-Filho, Aljomar José; da Silva Vieira Marques, Isabella; dos Santos, Daniela Micheline; Matos, Adaias Oliveira; Rangel, Elidiane Cipriano; da Cruz, Nilson Cristino; Barão, Valentim Adelino Ricardo

    2016-03-01

    The effect of nonthermal plasma on the surface characteristics of commercially pure titanium (cp-Ti), and on the shear bond strength between an autopolymerizing acrylic resin and cp-Ti was investigated. A total of 96 discs of cp-Ti were distributed into four groups (n=24): Po (no surface treatment), SB (sandblasting), Po+NTP and SB+NTP (methane plasma). Surface characterization was performed through surface energy, surface roughness, scanning microscopy, energy dispersive spectroscopy, and X-ray diffraction tests. Shear bond strength test was conducted immediately and after thermocycling. Surface treatment affected the surface energy and roughness of cp-Ti discs (P<.001). SEM-EDS showed the presence of the carbide thin film. XRD spectra revealed no crystalline phase changes. The SB+NTP group showed the highest bond strength values (6.76±0.70 MPa). Thermocycling reduced the bond strength of the acrylic resin/cp-Ti interface (P<.05), except for Po group. NTP is an effective treatment option for improving the shear bond strength between both materials. PMID:26706504

  9. Amphoteric Aqueous Hafnium Cluster Chemistry.

    Science.gov (United States)

    Goberna-Ferrón, Sara; Park, Deok-Hie; Amador, Jenn M; Keszler, Douglas A; Nyman, May

    2016-05-17

    Selective dissolution of hafnium-peroxo-sulfate films in aqueous tetramethylammonium hydroxide enables extreme UV lithographic patterning of sub-10 nm HfO2 structures. Hafnium speciation under these basic conditions (pH>10), however, is unknown, as studies of hafnium aqueous chemistry have been limited to acid. Here, we report synthesis, crystal growth, and structural characterization of the first polynuclear hydroxo hafnium cluster isolated from base, [TMA]6 [Hf6 (μ-O2 )6 (μ-OH)6 (OH)12 ]⋅38 H2 O. The solution behavior of the cluster, including supramolecular assembly via hydrogen bonding is detailed via small-angle X-ray scattering (SAXS) and electrospray ionization mass spectrometry (ESI-MS). The study opens a new chapter in the aqueous chemistry of hafnium, exemplifying the concept of amphoteric clusters and informing a critical process in single-digit-nm lithography. PMID:27094575

  10. Substituent-controlled selective synthesis of N-acyl 2-aminothiazoles by intramolecular Zwitterion-mediated C-N bond cleavage.

    Science.gov (United States)

    Wang, Yang; Zhao, Fei; Chi, Yue; Zhang, Wen-Xiong; Xi, Zhenfeng

    2014-11-21

    The cleavage of C-N bonds is an interesting and challenging subject in modern organic synthesis. We have achieved the first zwitterion-controlled C-N bond cleavage in the MCR reaction among lithium alkynethiolates, bulky carbodiimides, and acid chlorides to construct N-acyl 2-aminothiazoles. This is a simple, highly efficient, and general method for the preparation of N-acyl 2-aminothiazoles with a broad range of substituents. The selective synthesis of N-acyl 2-aminothiazoles significantly depends on the steric hindrance of carbodiimides. The result is in striking contrast with our previous convergent reaction giving 5-acyl-2-iminothiazolines via 1,5-acyl migration. It is indeed interesting that the slight change of the substituents on the carbodiimides can completely switch the product structure. Experimental and theoretical results demonstrate the reason why the C-N bond cleavage in the present system is prior to the acyl migration. The intramolecular hydrogen relay via unprecedented Hofmann-type elimination is essential for this totally new zwitterion-controlled C-N bond cleavage.

  11. Bonds Between Atoms.

    Science.gov (United States)

    Holden, Alan

    The field of inquiry into how atoms are bonded together to form molecules and solids crosses the borderlines between physics and chemistry encompassing methods characteristic of both sciences. At one extreme, the inquiry is pursued with care and rigor into the simplest cases; at the other extreme, suggestions derived from the more careful inquiry…

  12. Control of HOD photodissociation dynamics via bond-selective infrared multiphoton excitation and a femtosecond ultraviolet laser pulse

    DEFF Research Database (Denmark)

    Amstrup, Bjarne; Henriksen, Niels Engholm

    1992-01-01

    A scheme for controlling the outcome of a photodissociation process is studied. It involves two lasers—one intense laser in the infrared region which is supposed to excite a particular bond in the electronic ground state, and a second short laser pulse in the ultraviolet region which, at the righ...

  13. The influence of four dual-cure resin cements and surface treatment selection to bond strength of fiber post

    Institute of Scientific and Technical Information of China (English)

    Chang Liu; Hong Liu; Yue-Tong Qian; Song Zhu; Su-Qian Zhao

    2014-01-01

    In this study, we evaluate the influence of post surface pre-treatments on the bond strength of four different cements to glass fiber posts. Eighty extracted human maxillary central incisors and canines were endodontically treated and standardized post spaces were prepared. Four post pre-treatments were tested:(i) no pre-treatment (NS, control), (ii) sandblasting (SA), (iii) silanization (SI) and (iv) sandblasting followed by silanization (SS). Per pre-treatment, four dual-cure resin cements were used for luting posts:DMG LUXACORE Smartmix Dual, Multilink Automix, RelyX Unicem and Panavia F2.0. All the specimens were subjected to micro push-out test. Two-way analysis of variance and Tukey post hoc tests were performed (a50.05) to analyze the data. Bond strength was significantly affected by the type of resin cement, and bond strengths of RelyX Unicem and Panavia F2.0 to the fiber posts were significantly higher than the other cement groups. Sandblasting significantly increased the bond strength of DMG group to the fiber posts.

  14. Quantum chemistry

    CERN Document Server

    Lowe, John P

    2006-01-01

    Lowe's new edition assumes little mathematical or physical sophistication and emphasizes an understanding of the techniques and results of quantum chemistry. It can serve as a primary text in quantum chemistry courses, and enables students and researchers to comprehend the current literature. This third edition has been thoroughly updated and includes numerous new exercises to facilitate self-study and solutions to selected exercises.* Assumes little initial mathematical or physical sophistication, developing insights and abilities in the context of actual problems* Provides thorough treatment

  15. Structural Criteria for the Rational Design of Selective Ligands: Convergent Hydrogen Bonding Sites for the Nitrate Anion

    Energy Technology Data Exchange (ETDEWEB)

    Hay, Benjamin P.; Gutowski, Maciej S.; Dixon, David A.; Garza , Jorge; Vargas, Rubicelia; Moyer, Bruce A.

    2004-06-30

    Molecular hosts for anion complexation are often constructed by combining two or more hydrogen bonding functional groups, D–H. The deliberate design of complementary host architectures requires knowledge of the optimal geometry for the hydrogen bonds formed between the host and the guest. Herein, we present a detailed study of the structural aspects of hydrogen bonding interactions with the NO3– anion. A large number of crystal structures are analyzed to determine the number of hydrogen bond contacts per anion and to further characterize the structural aspects of these interactions. Electronic structure calculations are used to determine stable geometries and interaction energies for NO3– complexes with several simple molecules possessing D–H groups, including water, methanol, N-methylformamide, and methane. Theoretical results are reported at several levels of density functional theory, including BP86/DN**, B3LYP/TZVP, and B3LYP/TZVP+, and at MP2/aug-cc-pVDZ. In addition, MP2 binding energies for these complexes were obtained at the complete basis set limit by extrapolating from single point energies obtained with larger correlation-consistent basis sets. The results establish that NO3– has an intrinsic hydrogen bonding topography in which there are six optimal sites for proton location. The structural features observed in crystal structures and in the optimized geometries of complexes are explained by a preference to locate the D–H protons in these positions. For the strongest hydrogen bonding interactions, the N–O•••H angle is bent at an angle of 115 ± 10°, and the hydrogen atom lies in the NO3– plane giving O–N–O•••H dihedral angles of 0 and 180°. In addition, the D-H vector points towards the oxygen atom, giving D–H•••O angles that are near linear, 170 ± 10°. Due to steric hindrance, simple alcohol O–H and amide N–H donors form 3:1 complexes with NO3–, with H•••O distances of 1.85 ± 0.5 Å. Thus, the

  16. Hydrogen Bonds Involving Metal Centers

    OpenAIRE

    Pavlović, G.; Raos, N.

    2006-01-01

    Hydrogen bonds involving metal center as a hydrogen donor or hydrogen acceptor are only a specific type of metal-hydrogen interactions; it is therefore not easy to differentiate hydrogen bond from other metal-hydrogen interactions, especially agostic ones. The first part of the review is therefore devoted to the results of structural chemistry and molecular spectroscopy (NMR, IR), as a tool for differentiating hydrogen bondings from other hydrogen interactions. The classical examples of Pt···...

  17. Organic chemistry experiment

    Energy Technology Data Exchange (ETDEWEB)

    Mun, Seok Sik

    2005-02-15

    This book deals with organic chemistry experiments, it is divided five chapters, which have introduction, the way to write the experiment report and safety in the laboratory, basic experiment technic like recrystallization and extraction, a lot of organic chemistry experiments such as fischer esterification, ester hydrolysis, electrophilic aromatic substitution, aldol reaction, benzoin condensation, wittig reaction grignard reaction, epoxidation reaction and selective reduction. The last chapter introduces chemistry site on the internet and way to find out reference on chemistry.

  18. The influence of four dual-cure resin cements and surface treatment selection to bond strength of fiber post

    OpenAIRE

    Liu, Chang; Liu, Hong; Qian, Yue-Tong; Zhu, Song; Zhao, Su-Qian

    2013-01-01

    In this study, we evaluate the influence of post surface pre-treatments on the bond strength of four different cements to glass fiber posts. Eighty extracted human maxillary central incisors and canines were endodontically treated and standardized post spaces were prepared. Four post pre-treatments were tested: (i) no pre-treatment (NS, control), (ii) sandblasting (SA), (iii) silanization (SI) and (iv) sandblasting followed by silanization (SS). Per pre-treatment, four dual-cure resin cements...

  19. Mechanisms of Selective Cleavage of C-O Bonds in Di-aryl Ethers in Aqueous Phase

    Energy Technology Data Exchange (ETDEWEB)

    He, Jiayue; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

    2014-01-02

    A novel route for cleaving the C-O aryl ether bonds of p-substituted H-, CH3-, and OH- diphenyl ethers has been explored over Ni/SiO2 catalysts at very mild conditions. The C-O bond of diphenyl ether is cleaved by parallel hydrogenolysis and hydrolysis (hydrogenolysis combined with HO* addition) on Ni. The rates as a function of H2 pressure from 0 to 10 MPa indicate that the rate-determining step is the C-O bond cleavage on Ni. H* atoms compete with the organic reactant for adsorption leading to a maximum in the rate with increasing H2 pressure. In contrast to diphenyl ether, hydrogenolysis is the exclusive route for cleaving an ether C-O bond of di-p-tolyl ether to form p-cresol and toluene. 4,4'-dihydroxydiphenyl ether undergoes sequential surface hydrogenolysis, first to phenol and HOC6H4O* (adsorbed), which is then cleaved to phenol (C6H5O* with added H*) and H2O (O* with two added H*) in a second step. Density function theory supports the operation of this pathway. Notably, addition of H* to HOC6H4O* is less favorable than a further hydrogenolytic C-O bond cleavage. The TOFs of three aryl ethers with Ni/SiO2 in water followed the order 4,4'-dihydroxydiphenyl ether (69 h-1) > diphenyl ether (26 h-1) > di-p-tolyl ether (1.3 h-1), in line with the increasing apparent activation energies, ranging from 93 kJ∙mol-1 (4,4'-dihydroxydiphenyl ether) < diphenyl ether (98 kJ∙mol-1) to di-p-tolyl ether (105 kJ∙mol-1). D.M. thanks the support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the

  20. Surface-Controlled Mono/Diselective ortho C-H Bond Activation.

    Science.gov (United States)

    Li, Qing; Yang, Biao; Lin, Haiping; Aghdassi, Nabi; Miao, Kangjian; Zhang, Junjie; Zhang, Haiming; Li, Youyong; Duhm, Steffen; Fan, Jian; Chi, Lifeng

    2016-03-01

    One of the most charming and challenging topics in organic chemistry is the selective C-H bond activation. The difficulty arises not only from the relatively large bond-dissociation enthalpy, but also from the poor reaction selectivity. In this work, Au(111) and Ag(111) surfaces were used to address ortho C-H functionalization and ortho-ortho couplings of phenol derivatives. More importantly, the competition between dehydrogenation and deoxygenation drove the diversity of reaction pathways of phenols on surfaces, that is, diselective ortho C-H bond activation on Au(111) surfaces and monoselective ortho C-H bond activation on Ag(111) surfaces. The mechanism of this unprecedented phenomenon was extensively explored by scanning tunneling microscopy, density function theory, and X-ray photoelectron spectroscopy. Our findings provide new pathways for surface-assisted organic synthesis via the mono/diselective C-H bond activation. PMID:26853936

  1. Computational chemistry

    Science.gov (United States)

    Arnold, J. O.

    1987-01-01

    With the advent of supercomputers, modern computational chemistry algorithms and codes, a powerful tool was created to help fill NASA's continuing need for information on the properties of matter in hostile or unusual environments. Computational resources provided under the National Aerodynamics Simulator (NAS) program were a cornerstone for recent advancements in this field. Properties of gases, materials, and their interactions can be determined from solutions of the governing equations. In the case of gases, for example, radiative transition probabilites per particle, bond-dissociation energies, and rates of simple chemical reactions can be determined computationally as reliably as from experiment. The data are proving to be quite valuable in providing inputs to real-gas flow simulation codes used to compute aerothermodynamic loads on NASA's aeroassist orbital transfer vehicles and a host of problems related to the National Aerospace Plane Program. Although more approximate, similar solutions can be obtained for ensembles of atoms simulating small particles of materials with and without the presence of gases. Computational chemistry has application in studying catalysis, properties of polymers, all of interest to various NASA missions, including those previously mentioned. In addition to discussing these applications of computational chemistry within NASA, the governing equations and the need for supercomputers for their solution is outlined.

  2. Novel mononuclear vanadium complexes having pentalene ligands η8-bonded to a single metal atom - a new type of coordination in organometallic chemistry

    International Nuclear Information System (INIS)

    The pronounced folding of the η8-coordinated pentalene ligand along the bond between the two bridgehead carbon atoms is the most prominent structural feature of the vanadium complex 2. This compound and further 18e complexes of this type are readily prepared by the reaction of vanadocene monohalides 1 or their derivatives with dilithium pentalenediide. Although these mononuclear complexes are air-sensitive, they are thermally so stable that they can be sublimed in high vacuum at 80-100 C without decomposition. (orig.)

  3. Novel mononuclear vanadium complexes having pentalene ligands {eta}{sup 8}-bonded to a single metal atom - a new type of coordination in organometallic chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Jonas, K.; Gabor, B.; Mynott, R.; Angermund, K.; Heinemann, O.; Krueger, C. [Max-Planck-Institut fuer Kohlenforschung, Muelheim an der Ruhr (Germany)

    1997-09-01

    The pronounced folding of the {eta}{sup 8}-coordinated pentalene ligand along the bond between the two bridgehead carbon atoms is the most prominent structural feature of the vanadium complex 2. This compound and further 18e complexes of this type are readily prepared by the reaction of vanadocene monohalides 1 or their derivatives with dilithium pentalenediide. Although these mononuclear complexes are air-sensitive, they are thermally so stable that they can be sublimed in high vacuum at 80-100 C without decomposition. (orig.)

  4. Interfacial bonding enhancement of reel-to-reel selective electrodeposition of copper stabilizer on a multifilamentary second-generation high-temperature superconductor tape

    Science.gov (United States)

    Cai, Xinwei; Li, Wei; Bose, Anima; Selvamanickam, Venkat

    2016-10-01

    A reel-to-reel copper selective electrodeposition process over a multifilamentary second-generation high-temperature superconductor (2G-HTS) has been demonstrated in our previous work. If the interfacial bonding between the deposited copper layer and the underlying silver overlayer is weak, it might lead to delamination in applications including magnets, motors and generators. In this study, two approaches have been used to improve the copper-silver bonding without the degradation of superconductor performance. The first approach is acidifying the electrolyte by adding sulfuric acid, by which the kinetics of copper electrodeposition is enhanced, resulting in finer microstructure at the copper-silver interface and thus, improved interfacial bonding strength. The second approach consists of blocking the electrolyte outflow at the entrance of the reel-to-reel electroplating cell, by which the occurrence of large copper seeds on the tape caused by the heavy turbulence flow is effectively prevented. With these two improvements together deployed in the process, the peeling strength between the copper and silver layers of the 2G-HTS tape has been improved from 2 N in 90° peeling and from 3.0 N in 180° peeling, without any degradation on the superconducting performance.

  5. C-H bond activation by f-block complexes.

    Science.gov (United States)

    Arnold, Polly L; McMullon, Max W; Rieb, Julia; Kühn, Fritz E

    2015-01-01

    Most homogeneous catalysis relies on the design of metal complexes to trap and convert substrates or small molecules to value-added products. Organometallic lanthanide compounds first gave a tantalizing glimpse of their potential for catalytic C-H bond transformations with the selective cleavage of one C-H bond in methane by bis(permethylcyclopentadienyl)lanthanide methyl [(η(5) -C5 Me5 )2 Ln(CH3 )] complexes some 25 years ago. Since then, numerous metal complexes from across the periodic table have been shown to selectively activate hydrocarbon C-H bonds, but the challenges of closing catalytic cycles still remain; many f-block complexes show great potential in this important area of chemistry. PMID:25384554

  6. Selectivity of Chemisorbed Oxygen in C–H Bond Activation and CO Oxidation and Kinetic Consequences for CH₄–O₂ Catalysis on Pt and Rh Clusters

    Energy Technology Data Exchange (ETDEWEB)

    Chin, Ya-Huei; Buda, Corneliu; Neurock, Matthew; Iglesia, Enrique

    2011-10-06

    Rate measurements, density functional theory (DFT) within the framework of transition state theory, and ensemble-averaging methods are used to probe oxygen selectivities, defined as the reaction probability ratios for O* reactions with CO and CH₄, during CH₄–O₂ catalysis on Pt and Rh clusters. CO₂ and H₂O are the predominant products, but small amounts of CO form as chemisorbed oxygen atoms (O*) are depleted from cluster surfaces. Oxygen selectivities, measured using ¹²CO–¹³CH₄–O₂ reactants, increase with O₂/ CO ratio and O* coverage and are much larger than unity at all conditions on Pt clusters. These results suggest that O* reacts much faster with CO than with CH₄, causing any CO that forms and desorbs from metal cluster surfaces to react along the reactor bed with other O* to produce CO₂ at any residence time required for detectable extents of CH₄ conversion. O* selectivities were also calculated by averaging DFTderived activation barriers for CO and CH₄ oxidation reactions over all distinct surface sites on cubo-octahedral Pt clusters (1.8 nm diameter, 201 Pt atoms) at low O* coverages, which are prevalent at low O₂ pressures during catalysis. CO oxidation involves non-activated molecular CO adsorption as the kinetically relevant step on exposed Pt atoms vicinal of chemisorbed O* atoms (on *–O* site pairs). CH₄ oxidation occurs via kinetically relevant C–H bond activation on *–* site pairs involving oxidative insertion of a Pt atom into one of the C–H bonds in CH₄, forming a three-centered HC₃–Pt–H transition state. C–H bond activation barriers reflect the strength of Pt–CH₃ and Pt–H interactions at the transition state, which correlates, in turn, with the Pt coordination and with CH₃ * binding energies. Ensemble-averaged O* selectivities increase linearly with O₂/CO ratios, which define the O* coverages, via a proportionality constant. The proportionality constant is given by the ratio of rate

  7. Comparative analysis of a nontraditional general chemistry textbook and selected traditional textbooks used in Texas community colleges

    Science.gov (United States)

    Salvato, Steven Walter

    The purpose of this study was to analyze questions within the chapters of a nontraditional general chemistry textbook and the four general chemistry textbooks most widely used by Texas community colleges in order to determine if the questions require higher- or lower-order thinking according to Bloom's taxonomy. The study employed quantitative methods. Bloom's taxonomy (Bloom, Engelhart, Furst, Hill, & Krathwohl, 1956) was utilized as the main instrument in the study. Additional tools were used to help classify the questions into the proper category of the taxonomy (McBeath, 1992; Metfessel, Michael, & Kirsner, 1969). The top four general chemistry textbooks used in Texas community colleges and Chemistry: A Project of the American Chemical Society (Bell et al., 2005) were analyzed during the fall semester of 2010 in order to categorize the questions within the chapters into one of the six levels of Bloom's taxonomy. Two coders were used to assess reliability. The data were analyzed using descriptive and inferential methods. The descriptive method involved calculation of the frequencies and percentages of coded questions from the books as belonging to the six categories of the taxonomy. Questions were dichotomized into higher- and lower-order thinking questions. The inferential methods involved chi-square tests of association to determine if there were statistically significant differences among the four traditional college general chemistry textbooks in the proportions of higher- and lower-order questions and if there were statistically significant differences between the nontraditional chemistry textbook and the four traditional general chemistry textbooks. Findings indicated statistically significant differences among the four textbooks frequently used in Texas community colleges in the number of higher- and lower-level questions. Statistically significant differences were also found among the four textbooks and the nontraditional textbook. After the analysis of

  8. The Application of SCC-DV-Xα Computational Method of Quantum Chemistry in Cement Chemistry

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    It has been explored why quantum chemistry is applied to the research field of cement chemistry. The fundamental theory of SCC-DV-Xα computational method of quantum chemistry is synopsized. The results obtained by computational quantum chemistry method in recent years of valence-bond structures and hydration activity of some cement clinker minerals, mechanical strength and stabilization of some hydrates are summarized and evaluated. Finally the prospects of the future application of quantum chemistry to cement chemistry are depicted.

  9. Exercises in Computational Chemistry

    DEFF Research Database (Denmark)

    Spanget-Larsen, Jens

    2016-01-01

    A selection of HyperChem© PC-exercises in computational chemistry. Answers to most questions are appended (Roskilde University 2014-16).......A selection of HyperChem© PC-exercises in computational chemistry. Answers to most questions are appended (Roskilde University 2014-16)....

  10. Application of mixed-mode, solid-phase extraction in environmental and clinical chemistry. Combining hydrogen-bonding, cation-exchange and Van der Waals interactions

    Science.gov (United States)

    Mills, M.S.; Thurman, E.M.; Pedersen, M.J.

    1993-01-01

    Silica- and styrene-divinylbenzene-based mixed-mode resins that contain C8, C18 and sulphonated cation-exchange groups were compared for their efficiency in isolation of neutral triazine compounds from water and of the basic drug, benzoylecgonine, from urine. The triazine compounds were isolated by a combination of Van der Waals and hydrogen-bonding interactions, and benzoylecgonine was isolated by Van der Waals interactions and cation exchange. All analytes were eluted with a polar organic solvent contaning 2% ammonium hydroxide. Larger recoveries (95%) were achieved on copolymerized mixed-mode resins where C18 and sulfonic acid are in closer proximity than on 'blended' mixed-mode resins (60-70% recovery).

  11. Probing the structures and chemical bonding of boron-boronyl clusters using photoelectron spectroscopy and computational chemistry: B4(BO)(n)- (n = 1-3).

    Science.gov (United States)

    Chen, Qiang; Zhai, Hua-Jin; Li, Si-Dian; Wang, Lai-Sheng

    2012-07-28

    The electronic and structural properties of a series of boron oxide clusters, B(5)O(-), B(6)O(2)(-), and B(7)O(3)(-), are studied using photoelectron spectroscopy and density functional calculations. Vibrationally resolved photoelectron spectra are obtained, yielding electron affinities of 3.45, 3.54, and 4.94 eV for the corresponding neutrals, B(5)O, B(6)O(2), and B(7)O(3), respectively. Structural optimizations show that these oxide clusters can be formulated as B(4)(BO)(n)(-) (n = 1-3), which involve boronyls coordinated to a planar rhombic B(4) cluster. Chemical bonding analyses indicate that the B(4)(BO)(n)(-) clusters are all aromatic species with two π electrons. PMID:22852618

  12. Comparison of select hematology and serum chemistry analtyes between wild-caught and aquarium-housed lake sturgeon (Acipenser fulvescens)

    Science.gov (United States)

    DiVincenti, Louis; Priest, Heather; Walker, Kyle J.; Wyatt, Jeffrey D.; Dittman, Dawn

    2013-01-01

    Hematology and serum chemistry analytes were compared between wild-caught and aquarium-housed lake sturgeon (Acipenser fulvescens) to potentially improve understanding of medical issues in lake sturgeon. Blood samples were taken from 30 lake sturgeon exhibited in 11 institutions in the United States and from 23 experimentally stocked lake sturgeon caught in gill nets in the lower Genesee River in Rochester, New York, USA. For hematology, only segmented neutrophil count was significantly different, with wild-caught fish having a higher number of circulating neutrophils. For clinical chemistry analytes, chloride, uric acid, calcium, phosphate, glucose, aspartate aminotransferase, triglycerides, and creatine kinase were significantly different between the two cohorts. These differences are likely not clinically significant and are attributable to handling stress, variability in environmental parameters, or differences in nutritional status. This is the first report of hematology and serum chemistry values in aquarium-housed lake sturgeon and provides useful reference intervals for clinicians.

  13. DOE fundamentals handbook: Chemistry

    International Nuclear Information System (INIS)

    The Chemistry Handbook was developed to assist nuclear facility operating contractors in providing operators, maintenance personnel, and the technical staff with the necessary fundamentals training to ensure a basic understanding of chemistry. The handbook includes information on the atomic structure of matter; chemical bonding; chemical equations; chemical interactions involved with corrosion processes; water chemistry control, including the principles of water treatment; the hazards of chemicals and gases, and basic gaseous diffusion processes. This information will provide personnel with a foundation for understanding the chemical properties of materials and the way these properties can impose limitations on the operation of equipment and systems

  14. Velocity Map Imaging Study of Ion-Radical Chemistry: Charge Transfer and Carbon-Carbon Bond Formation in the Reactions of Allyl Radicals with C(.).

    Science.gov (United States)

    Pei, Linsen; Farrar, James M

    2016-08-11

    We present an experimental and computational study of the dynamics of collisions of ground state carbon cations with allyl radicals, C3H5, at a collision energy of 2.2 eV. Charge transfer to produce the allyl cation, C3H5(+), is exoergic by 3.08 eV and proceeds via energy resonance such that the electron transfer occurs without a significant change in nuclear velocities. The products have sufficient energy to undergo the dissociation process C3H5(+) → C3H4(+) + H. Approximately 80% of the reaction products are ascribed to charge transfer, with ∼40% of those products decaying via loss of a hydrogen atom. We also observe products arising from the formation of new carbon-carbon bonds. The experimental velocity space flux distributions for the four-carbon products are symmetric about the centroid of the reactants, providing direct evidence that the products are mediated by formation of a C4H5(+) complex living at least a few rotational periods. The primary four-carbon reaction products are formed by elimination of molecular hydrogen from the C4H5(+) complex. More than 75% of the nascent C4H3(+) products decay by C-H bond cleavage to yield a C4H2(+) species. Quantum chemical calculations at the MP2/6-311+g(d,p) level of theory support the formation of a nonplanar cyclic C4H5(+) adduct that is produced when the p-orbital containing the unpaired electron on C(+) overlaps with the unpaired spin density on the terminal carbon atoms in allyl. Product formation then occurs by 1,2-elimination of molecular hydrogen from the cyclic intermediate to form a planar cyclic C4H3(+) product. The large rearrangement in geometry as the C4H3(+) products are formed is consistent with high vibrational excitation in that product and supports the observation that the majority of those products decay to form the C4H2(+) species. PMID:27434380

  15. Metalloradical-Catalyzed Selective 1,2-Rh-H Insertion into the Aliphatic Carbon-Carbon Bond of Cyclooctane

    NARCIS (Netherlands)

    Y.W. Chan; B. de Bruin; K.S. Chan

    2015-01-01

    The selective aliphatic carboncarbon activation of cyclo-octane (c-octane) was achieved via the Rh-II(ttp)-catalyzed 1,2-addition of Rh(ttp)H to give Rh(ttp)(n-octyl) (ttp = tetratolylporphyrinato dianion) in good yield under mild reaction conditions. This mechanism is further supported by DFT calcu

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

    International Nuclear Information System (INIS)

    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 Yb3+-doped materials for high-power laser applications, shows that simple oxides containing rare-earths are favorable. Therefore, the spectroscopic properties of six new materials Yb3+:GdVO4, Yb3+:GdAlO3, Yb3+:Gd2O3, Yb3+:Sc2SiO5, Yb3+:CaSc2O4 and Yb3+:SrSc2O4 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 Yb3+:BOYS, a largely-tunable laser material which is of great interest for femtosecond pulses generation. (author)

  17. Shape-selective catalysts for Fischer-Tropsch chemistry. Final report : January 1, 2001 - December 31, 2008.

    Energy Technology Data Exchange (ETDEWEB)

    Cronauer, D. C. (Chemical Sciences and Engineering Division)

    2011-04-11

    Argonne National Laboratory carried out a research program to create, prepare, and evaluate catalysts to promote Fischer-Tropsch (FT) chemistry-specifically, the reaction of hydrogen with carbon monoxide to form long-chain hydrocarbons. In addition to needing high activity, it was desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. It was desired that selectivity be directed toward producing diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. The original goal was to produce shape-selective catalysts that had the potential to limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' This cage would also restrict their loss by attrition during use in slurry-bed reactors. The first stage of this program was to prepare and evaluate iron-containing particulate catalysts. Such catalysts were prepared with silica-containing fractal cages. The activity and strength was essentially the same as that of catalysts without the cages. Since there was no improvement, the program plan was modified as discussed below. A second experimental stage was undertaken to prepare and evaluate active FT catalysts formed by atomic-layer deposition [ALD] of active components on supported membranes and particulate supports. The concept was that of depositing active metals (i.e. ruthenium, iron or cobalt) upon membranes with well defined flow channels of small diameter and length such that the catalytic activity and product molecular weight distribution could be controlled. In order to rapidly evaluate the catalytic membranes, the ALD coating processes were performed in an 'exploratory mode' in which ALD procedures from the literature appropriate for coating flat surfaces were applied to the high surface area membranes. Consequently, the Fe and Ru loadings in the membranes were likely to be smaller than those

  18. Selected clinical chemistry analytes correlate with the pathogenesis of inclusion body hepatitis experimentally induced by fowl aviadenoviruses.

    Science.gov (United States)

    Matos, Miguel; Grafl, Beatrice; Liebhart, Dieter; Schwendenwein, Ilse; Hess, Michael

    2016-10-01

    In the present study, clinical chemistry was applied to assess the pathogenesis and progression of experimentally induced inclusion body hepatitis (IBH). For this, five fowl aviadenovirus (FAdV) strains from recent IBH field outbreaks were used to orally inoculate different groups of day-old specific pathogen-free chickens, which were weighed, sampled and examined during necropsy by sequential killing. Mortalities of 50% and 30% were recorded in two groups between 6 and 9 days post-infection (dpi), along with a decreased weight of 23% and 20%, respectively, compared to the control group. Macroscopical changes were seen in the liver and kidney between 6 and 10 dpi, with no lesions being observed in the other organs. Histological lesions were observed in the liver and pancreas during the same period. Plasma was collected from killed birds of each group at each time point and the following clinical chemistry analytes were investigated: aspartate aminotransferase (AST), glutamate dehydrogenase (GLDH), bile acids, total protein, albumin, uric acid and lipase. Plasma protein profile, AST and GLDH, together with bile acids values paralleled the macroscopical and histopathological lesions in the liver, while plasma lipase activity levels coincided with lesions observed in pancreas. In agreement with the histology and clinical chemistry, viral load in the target organs, liver and pancreas, was highest at 7 dpi. Thus, clinical chemistry was found to be a valuable tool in evaluating and monitoring the progression of IBH in experimentally infected birds, providing a deeper knowledge of the underlying pathophysiological mechanisms of a FAdV infection in chickens.

  19. Bond Issues.

    Science.gov (United States)

    Pollack, Rachel H.

    2000-01-01

    Notes trends toward increased borrowing by colleges and universities and offers guidelines for institutions that are considering issuing bonds to raise money for capital projects. Discussion covers advantages of using bond financing, how use of bonds impacts on traditional fund raising, other cautions and concerns, and some troubling aspects of…

  20. An in vitro compartmentalization-based method for the selection of bond-forming enzymes from large libraries.

    Science.gov (United States)

    Gianella, Paul; Snapp, Erik L; Levy, Matthew

    2016-08-01

    We have developed a generalized in vitro compartmentalization-based bead display selection strategy that allows for the identification of enzymes that can perform ligation reactions. Although a number of methods have been developed to evolve such enzymes, many of them are limited in library size (10(6) -10(7) ), do not select for enzymes using a scheme that allows for multiple turnover, or only work on enzymes specific to nucleic acids. This approach is amenable to screening libraries of up to 10(12) protein variants by allowing beads to be overloaded with up to 10(4) unique mutants. Using this approach we isolated a variant of sortase A from Staphylococcus aureus that shows a 114-fold enhancement in kcat /KM in the absence of calcium compared to the wild-type and improved resistance to the inhibitory effects of cell lysates. Unlike the wild-type protein, the newly selected variant shows intracellular activity in the cytoplasm of eukaryotic cells where it may prove useful for intracellular labeling or synthetic biological applications. Biotechnol. Bioeng. 2016;113: 1647-1657. © 2016 Wiley Periodicals, Inc. PMID:26806853

  1. Free-Radical Triggered Ordered Domino Reaction: An Approach to C-C Bond Formation via Selective Functionalization of α-Hydroxyl-(sp(3))C-H in Fluorinated Alcohols.

    Science.gov (United States)

    Xu, Zhengbao; Hang, Zhaojia; Liu, Zhong-Quan

    2016-09-16

    A free-radical mediated highly ordered radical addition/cyclization/(sp(3))C-C(sp(3)) formation domino reaction is developed. Three new C-C bonds are formed one by one in a mixed system. Furthermore, it represents the first example of cascade C-C bond formation via selective functionalization of α-hydroxyl-C(sp(3))-H in fluorinated alcohols.

  2. Uranium triamidoamine chemistry.

    Science.gov (United States)

    Gardner, Benedict M; Liddle, Stephen T

    2015-07-01

    Triamidoamine (Tren) complexes of the p- and d-block elements have been well-studied, and they display a diverse array of chemistry of academic, industrial and biological significance. Such in-depth investigations are not as widespread for Tren complexes of uranium, despite the general drive to better understand the chemical behaviour of uranium by virtue of its fundamental position within the nuclear sector. However, the chemistry of Tren-uranium complexes is characterised by the ability to stabilise otherwise reactive, multiply bonded main group donor atom ligands, construct uranium-metal bonds, promote small molecule activation, and support single molecule magnetism, all of which exploit the steric, electronic, thermodynamic and kinetic features of the Tren ligand system. This Feature Article presents a current account of the chemistry of Tren-uranium complexes.

  3. Selecting ethanol as a model organic solvent in radiation chemistry--3. Radiolysis of glycyrrhetinic acid (GL)-ethanol system and structure modification of GL by γ radiation method

    International Nuclear Information System (INIS)

    CH3CHOH, H·, esolv- are the main active radicals in the ethanol system irradiated by γ-ray without the presence of oxygen. In this study, GL ethanolic solution saturated with nitrogen was γ-irradiated, the radiolytic products were isolated by HPLC and the molecular structure was determined with UV, IR, MS spectra and elementary analysis methods. In this system GL reacts with H· and CH3CHOH radicals. CH3CHOH adds to the C-C double bond of GL, then the formed radicals disproportionate to the final products RP1 (olean 29-oic acid,3-hydroxy-11-oxo-12-ethoxyl-13-hydro-,(3β, 20β)-) and RP3. H· reacts with GL in the similar way. The rate constant of H· reacting with GL was obtained as kGL+H·=2.0x1010 dm3 mol-1 s-1. The rate constant of CH3CHOH reacting with GL was calculated as result of (1.2±0.1)x104 dm3 mol-1 s-1 by using steady state method and by using the numerical quadrature method with computer. G(-GL), G(H2 ), G(2,3-butanediol), G(CH3CHO) and G values of the radiolytic products of ethanolic solution with different GL concentration were measured. A material balance was obtained. Results show that the active site of a GL molecule is the C-C double bond. The radiation chemistry technique can be used to modify the structure of glycyrrhetinic acid

  4. Bad chemistry

    OpenAIRE

    Petsko, Gregory A

    2004-01-01

    General chemistry courses haven't changed significantly in forty years. Because most basic chemistry students are premedical students, medical schools have enormous influence and could help us start all over again to create undergraduate chemistry education that works.

  5. Hydrodenitrogenation chemistry. I. Cleavage of alkylcarbon-nitrogen bonds, methane and ammonia formation in the HDN reaction of 1,2,3,4-tetrahydroquinoline with a nickel oxide catalyst supported on silica/alumina

    Energy Technology Data Exchange (ETDEWEB)

    Fish, R.H.; Thormodsen, A.D.; Moore, R.S.; Perry, D.L.; Heinemann, H.

    1986-11-01

    The hydrodenitrogenation reaction (HDN) is one of the most important industrial processes used in the refining of petroleum feedstocks and involves the removal of the nitrogen atom, as ammonia, from polynuclear heteroaromatic nitrogen compounds at high temperatures and high pressures of hydrogen gas (350-500/sup 0/C and 2000 psi). It is interesting to note that most of the reported heterogeneous catalysts require the complete hydrogenation of both the nitrogen heterocyclic ring and the aromatic ring before carbon-nitrogen bond cleavage can occur. A major breakthrough in the technical and economic aspects of the HDN reaction would take place if, in fact a catalyst could be found that would selectively cleave the C-N bond din the saturated nitrogen ring and subsequently produce ammonia, without substantial reduction of the aromatic rings, at lower temperatures as well as lower pressures of hydrogen gas. In this note, the authors report on a highly loaded nickel oxide catalyst (50% by weight Ni), supported on silica/alumina, that will effectively provide some of the criteria for an ideal HDN catalyst. 8 references.

  6. Activation of B-H, Si-H, and C-F bonds with Tp'Rh(PMe3) complexes: kinetics, mechanism, and selectivity.

    Science.gov (United States)

    Procacci, Barbara; Jiao, Yunzhe; Evans, Meagan E; Jones, William D; Perutz, Robin N; Whitwood, Adrian C

    2015-01-28

    The photochemical reactions of Tp'Rh(PMe3)H2 (1) and thermal reactions of Tp'Rh(PMe3)(CH3)H (1a, Tp' = tris(3,5-dimethylpyrazolyl)borate) with substrates containing B-H, Si-H, C-F, and C-H bonds are reported. Complexes 1 and 1a are known activators of C-H bonds, including those of alkanes. Kinetic studies of reactions with HBpin and PhSiH3 show that photodissociation of H2 from 1 occurs prior to substrate attack, whereas thermal reaction of 1a proceeds by bimolecular reaction with the substrate. Complete intramolecular selectivity for B-H over C-H activation of HBpin (pin = pinacolate) leading to Tp'Rh(PMe3)(Bpin)H is observed. Similarly, the reaction with Et2SiH2 shows a strong preference for Si-H over C-H activation, generating Tp'Rh(PMe3)(SiEt2H)H. The Rh(Bpin)H and Rh(SiEt2H)H products were stable to heating in benzene in accord with DFT calculations that showed that reaction with benzene is endoergic. The intramolecular competition with PhSiH3 yields a ∼1:4 mixture of Tp'Rh(PMe3)(C6H4SiH3)H and Tp'Rh(PMe3)(SiPhH2)H, respectively. Reaction with pentafluoropyridine generates Tp'Rh(PMe3)(C5NF4)F, while reaction with 2,3,5,6-tetrafluoropyridine yields a mixture of C-H and C-F activated products. Hexafluorobenzene proves unreactive. Crystal structures are reported for B-H, Si-H, and C-F activated products, but in the latter case a bifluoride complex Tp'Rh(PMe3)(C5NF4)(FHF) was crystallized. Intermolecular competition reactions were studied by photoreaction of 1 in C6F6 with benzene and another substrate (HBpin, PhSiH3, or pentafluoropyridine) employing in situ laser photolysis in the NMR probe, resulting in a wide-ranging map of kinetic selectivities. The mechanisms of intramolecular and intermolecular selection are analyzed.

  7. Facile Isolation of Adsorbent-Free Long and Highly-Pure Chirality-Selected Semiconducting Single-Walled Carbon Nanotubes Using A Hydrogen-bonding Supramolecular Polymer

    Science.gov (United States)

    Toshimitsu, Fumiyuki; Nakashima, Naotoshi

    2015-12-01

    The ideal form of semiconducting-single-walled carbon nanotubes (sem-SWNTs) for science and technology is long, defect-free, chirality pure and chemically pure isolated narrow diameter tubes. While various techniques to solubilize and purify sem-SWNTs have been developed, many of them targeted only the chiral- or chemically-purity while sacrificing the sem-SWNT intrinsic structural identities by applying strong ultra-sonication and/or chemical modifications. Toward the ultimate purification of the sem-SWNTs, here we report a mild-conditioned extraction of the sem-SWNTs using removable supramolecular hydrogen-bonding polymers (HBPs) that are composed of dicarboxylic- or diaminopyridyl-fluorenes with ~70%-(8,6)SWNT selective extraction. Replacing conventional strong sonication techniques by a simple shaking using HPBs was found to provide long sem-SWNTs (>2.0 μm) with a very high D/G ratio, which was determined by atomic force microscopy observations. The HBPs were readily removed from the nanotube surfaces by an outer stimulus, such as a change in the solvent polarities, to provide chemically pure (8,6)-enriched sem-SWNTs. We also describe molecular mechanics calculations to propose possible structures for the HBP-wrapped sem-SWNTs, furthermore, the mechanism of the chiral selectivity for the sorted sem-SWNTs is well explained by the relationship between the molecular surface area and mass of the HBP/SWNT composites.

  8. 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.

  9. Beauty in chemistry

    Directory of Open Access Journals (Sweden)

    Peter Atkins

    2006-03-01

    Full Text Available Though hard going for the general reader and highly personal in its selectivity, Elegant Solutions: Ten Beautiful Experiments in Chemistry provides reflections of a thoughtful author that will delight chemists

  10. Beauty in chemistry

    OpenAIRE

    Peter Atkins

    2006-01-01

    Though hard going for the general reader and highly personal in its selectivity, Elegant Solutions: Ten Beautiful Experiments in Chemistry provides reflections of a thoughtful author that will delight chemists

  11. Cyclodextrin chemistry

    International Nuclear Information System (INIS)

    The chemistry of cyclodextrins was studied. This study included synthesising some cyclodextrin derivatives, preparing selected inclusion complexes with cyclodextrin and investigating the effects of gamma irradiation on cyclodextrins and certain linear oligosaccharides. This report presents a brief review of the structure and properties of cyclodextrins, the synthesis of cyclodextrin derivatives, their complexation and applications. This is followed by a description of the synthesis of some cyclodextrin derivatives and the preparation of inclusion complexes of cyclodextrin with some organic compounds. Finally, the effects of gamma irradiation on cyclodextrins, some of their derivatives and certain structurally related carbohydrates are discussed. The gamma irradiation studies were carried out for two reasons: to study the effects of gamma irradiation on cyclodextrins and their derivatives; and to investigate selectivity during the gamma irradiation of cyclodextrin derivatives

  12. Trends in lake chemistry in response to atmospheric deposition and climate in selected Class I wilderness areas in Colorado, Idaho, Utah, and Wyoming, 1993-2009

    Science.gov (United States)

    Mast, M. Alisa; Ingersoll, George P.

    2011-01-01

    In 2010, the U.S. Geological Survey, in cooperation with the U.S. Department of Agriculture Forest Service, Air Resource Management, began a study to evaluate long-term trends in lake-water chemistry for 64 high-elevation lakes in selected Class I wilderness areas in Colorado, Idaho, Utah, and Wyoming during 1993 to 2009. The purpose of this report is to describe trends in the chemical composition of these high-elevation lakes. Trends in emissions, atmospheric deposition, and climate variables (air temperature and precipitation amount) are evaluated over a similar period of record to determine likely drivers of changing lake chemistry. Sulfate concentrations in precipitation decreased over the past two decades at high-elevation monitoring stations in the Rocky Mountain region. The trend in deposition chemistry is consistent with regional declines in sulfur dioxide emissions resulting from installation of emission controls at large stationary sources. Trends in nitrogen deposition were not as widespread as those for sulfate. About one-half of monitoring stations showed increases in ammonium concentrations, but few showed significant changes in nitrate concentrations. Trends in nitrogen deposition appear to be inconsistent with available emission inventories, which indicate modest declines in nitrogen emissions in the Rocky Mountain region since the mid-1990s. This discrepancy may reflect uncertainties in emission inventories or changes in atmospheric transformations of nitrogen species that may be affecting deposition processes. Analysis of long-term climate records indicates that average annual mean air temperature minimums have increased from 0.57 to 0.75 °C per decade in mountain areas of the region with warming trends being more pronounced in Colorado. Trends in annual precipitation were not evident over the period 1990 to 2006, although wetter than average years during 1995 to 1997 and drier years during 2001 to 2004 caused a notable decline in precipitation

  13. Selective Catalytic Synthesis Using the Combination of Carbon Dioxide and Hydrogen: Catalytic Chess at the Interface of Energy and Chemistry.

    Science.gov (United States)

    Klankermayer, Jürgen; Wesselbaum, Sebastian; Beydoun, Kassem; Leitner, Walter

    2016-06-20

    The present Review highlights the challenges and opportunities when using the combination CO2 /H2 as a C1 synthon in catalytic reactions and processes. The transformations are classified according to the reduction level and the bond-forming processes, covering the value chain from high volume basic chemicals to complex molecules, including biologically active substances. Whereas some of these concepts can facilitate the transition of the energy system by harvesting renewable energy into chemical products, others provide options to reduce the environmental impact of chemical production already in today's petrochemical-based industry. Interdisciplinary fundamental research from chemists and chemical engineers can make important contributions to sustainable development at the interface of the energetic and chemical value chain. The present Review invites the reader to enjoy this exciting area of "catalytic chess" and maybe even to start playing some games in her or his laboratory. PMID:27237963

  14. Photoinduced hydrogen-bonding dynamics.

    Science.gov (United States)

    Chu, Tian-Shu; Xu, Jinmei

    2016-09-01

    Hydrogen bonding dynamics has received extensive research attention in recent years due to the significant advances in femtolaser spectroscopy experiments and quantum chemistry calculations. Usually, photoexcitation would cause changes in the hydrogen bonding formed through the interaction between hydrogen donor and acceptor molecules on their ground electronic states, and such transient strengthening or weakening of hydrogen bonding could be crucial for the photophysical transformations and the subsequent photochemical reactions that occurred on a time scale from tens of femtosecond to a few nanoseconds. In this article, we review the combined experimental and theoretical studies focusing on the ultrafast electronic and vibrational hydrogen bonding dynamics. Through these studies, new mechanisms and proposals and common rules have been put forward to advance our understanding of the hydrogen bondings dynamics in a variety of important photoinduced phenomena like photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer processes, chemosensor fluorescence sensing, rearrangements of the hydrogen-bond network including forming and breaking hydrogen bond in water. Graphical Abstract We review the recent advances on exploring the photoinduced hydrogen bonding dynamics in solutions through a joint approach of laser spectroscopy and theoretical calculation. The reviewed studies have put forward a new mechanism, new proposal, and new rule for a variety of photoinduced phenomena such as photosynthesis, dual fluorescence emission, rotational reorientation, excited-state proton transfer and charge transfer, chemosensor fluorescence sensing, and rearrangements of the hydrogen-bond network in water. PMID:27491849

  15. Upper Secondary Teachers' Knowledge for Teaching Chemical Bonding Models

    Science.gov (United States)

    Bergqvist, Anna; Drechsler, Michal; Chang Rundgren, Shu-Nu

    2016-01-01

    Researchers have shown a growing interest in science teachers' professional knowledge in recent decades. The article focuses on how chemistry teachers impart chemical bonding, one of the most important topics covered in upper secondary school chemistry courses. Chemical bonding is primarily taught using models, which are key for understanding…

  16. Principles of quantum chemistry

    CERN Document Server

    George, David V

    2013-01-01

    Principles of Quantum Chemistry focuses on the application of quantum mechanics in physical models and experiments of chemical systems.This book describes chemical bonding and its two specific problems - bonding in complexes and in conjugated organic molecules. The very basic theory of spectroscopy is also considered. Other topics include the early development of quantum theory; particle-in-a-box; general formulation of the theory of quantum mechanics; and treatment of angular momentum in quantum mechanics. The examples of solutions of Schroedinger equations; approximation methods in quantum c

  17. Organic chemistry: No double bond left behind

    Science.gov (United States)

    Sarlah, David

    2016-03-01

    Alkenyl halides are some of the most useful building blocks for synthesizing small organic molecules. A catalyst has now allowed their direct preparation from widely available alkenes using the cross-metathesis reaction. See Article p.459

  18. Mathematical Chemistry

    OpenAIRE

    Trinajstić, Nenad; Gutman, Ivan

    2002-01-01

    A brief description is given of the historical development of mathematics and chemistry. A path leading to the meeting of these two sciences is described. An attempt is made to define mathematical chemistry, and journals containing the term mathematical chemistry in their titles are noted. In conclusion, the statement is made that although chemistry is an experimental science aimed at preparing new compounds and materials, mathematics is very useful in chemistry, among other things, to produc...

  19. Analysis of Water-Quality Trends for Selected Streams in the Water Chemistry Monitoring Program, Michigan, 1998-2005

    Science.gov (United States)

    Hoard, C.J.; Fuller, Lori M.; Fogarty, Lisa R.

    2009-01-01

    In 1998, the Michigan Department of Environmental Quality and the U.S. Geological Survey began a long-term monitoring program to evaluate the water quality of most watersheds in Michigan. Major goals of this Water-Chemistry Monitoring Program were to identify streams exceeding or not meeting State or Federal water-quality standards and to assess if constituent concentrations reflecting water quality in these streams were increasing or decreasing over time. As part of this program, water-quality data collected from 1998 to 2005 were analyzed to identify potential trends. Sixteen water-quality constituents were analyzed at 31 sites across Michigan, 28 of which had sufficient data to analyze for trends. Trend analysis on the various water-quality data was done using the uncensored Seasonal Kendall test within the computer program ESTREND. The most prevalent trend detected throughout the state was for chloride. Chloride trends were detected at 8 of the 28 sites; trends at 7 sites were increasing and the trend at 1 site was decreasing. Although no trends were detected for various nitrogen species or phosphorus, these constituents were detected at levels greater than the U.S. Environmental Protection Agency recommendations for nutrients in water. The results of the trend analysis will help to establish a baseline to evaluate future changes in water quality in Michigan streams.

  20. Protein folding guides disulfide bond formation

    OpenAIRE

    Qin, Meng; Wang, Wei; Thirumalai, D.

    2015-01-01

    Anfinsen inferred the principles of protein folding by studying a protein containing four disulfide bonds in the native state. However, how protein folding drives disulfide bond formation is poorly understood despite the role such proteins play in variety of extracellular and intracellular functions. We developed a method to mimic the complex chemistry of disulfide bond formation in molecular simulations, which is used to decipher the mechanism of folding of bovine pancreatic trypsin inhibito...

  1. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen, and Zhejiang and Guangdong provinces to issue bonds for the first time. How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the ShanghaiSecuritiesJournal. Edited excerpts follow:

  2. Bond Boom

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    The Ministry of Finance recently kick-started a pilot program allowing local governments of Shanghai and Shenzhen,and Zhejiang and Guangdong provinces to issue bonds for the first time.How will the new policy affect fiscal capacities of local governments and the broader economy? What else should the country do to build a healthy bond market? Economists and experts discussed these issues in an interview with the Shanghai Securities Journal.Edited excerpts follow.

  3. Introductory quantum chemistry

    International Nuclear Information System (INIS)

    This book on quantum chemistry is primarily intended for university students at the senior undergraduate level. It serves as an aid to the basic understanding of the important concepts of quantum mechanics introduced in the field of chemistry. Various chapters of the book are devoted to the following : (i) Waves and quanta, (ii) Operator concept in quantum chemistry, (iii) Wave mechanics of some simple systems, (iv) Perturbation theory, (v) Many-electron atoms and angular momenta (vi) Molecular orbital theory and its application to the electronic structure of diatomic molecules, (vii) Chemical bonding in polyatomic molecules and (viii) Chemical applications of Hellmann-Feynman theorem. At the end of each chapter, a set of problems is given and the answers to these problems are given at the end of the book. (A.K.)

  4. Toward selective, sensitive, and discriminative detection of Hg(2+) and Cd(2+)via pH-modulated surface chemistry of glutathione-capped gold nanoclusters.

    Science.gov (United States)

    Huang, Pengcheng; Li, Sha; Gao, Nan; Wu, Fangying

    2015-11-01

    Heavy metal pollution can exert severe effects on the environment and human health. Simple, selective, and sensitive detection of heavy metal ions, especially two or more, using a single probe, is thereby of great importance. In this study, we report a new and facile strategy for discriminative detection of Hg(2+) and Cd(2+) with high selectivity and sensitivity via pH-modulated surface chemistry of the glutathione-capped gold NCs (GSH-Au NCs). By simply adjusting pH values of the colloidal solution of the NCs, Hg(2+) could specifically turn off the fluorescence under acidic pH, however, Cd(2+) could exclusively turn on the fluorescence under alkaline pH. This enables the NCs to serve as a dual fluorescent sensor for Hg(2+) and Cd(2+). We demonstrate that these two opposing sensing modes are presumably due to different interaction mechanisms: Hg(2+) induces aggregation by dissociating GSH from the Au surface via robust coordination and, Cd(2+) could passivate the Au surface by forming a Cd-GSH complex with a compact structure. Finally, the present strategy is successfully exploited to separately determine Hg(2+) and Cd(2+) in environmental water samples. PMID:26347906

  5. Chemistry Notes

    Science.gov (United States)

    School Science Review, 1976

    1976-01-01

    Described are eight chemistry experiments and demonstrations applicable to introductory chemistry courses. Activities include: measure of lattice enthalpy, Le Chatelier's principle, decarboxylation of soap, use of pocket calculators in pH measurement, and making nylon. (SL)

  6. Colour Chemistry

    Science.gov (United States)

    Griffiths, J.; Rattee, I. D.

    1973-01-01

    Discusses the course offerings in pure color chemistry at two universities and the three main aspects of study: dyestuff chemistry, color measurement, and color application. Indicates that there exists a constant challenge to ingenuity in the subject discipline. (CC)

  7. Positronium chemistry

    CERN Document Server

    Green, James

    1964-01-01

    Positronium Chemistry focuses on the methodologies, reactions, processes, and transformations involved in positronium chemistry. The publication first offers information on positrons and positronium and experimental methods, including mesonic atoms, angular correlation measurements, annihilation spectra, and statistical errors in delayed coincidence measurements. The text then ponders on positrons in gases and solids. The manuscript takes a look at the theoretical chemistry of positronium and positronium chemistry in gases. Topics include quenching, annihilation spectrum, delayed coincidence

  8. Combinatorial chemistry

    DEFF Research Database (Denmark)

    Nielsen, John

    1994-01-01

    An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds.......An overview of combinatorial chemistry is presented. Combinatorial chemistry, sometimes referred to as `irrational drug design,' involves the generation of molecular diversity. The resulting chemical library is then screened for biologically active compounds....

  9. Infrared matrix isolation studies of hydrogen bonds involving C-H bonds: CF 3H, (CF 2H) 2O and CF 3OCF 2H with selected bases

    Science.gov (United States)

    Jeng, Mei-Lee H.; Ault, Bruce S.

    1991-06-01

    Hydrogen bonded complexes of fluoroform and fluoromethylethers with halide anions and amines have been isolated at 15 K in argon matrices and characterized by IR spectroscopy. The observed red shifts of the CH stretching mode were significantly less than for analogous alkyne complexes. For a given alkane, the magnitude of shifts for complexes with the halide anions were greater than complexes with neutral amines, consistent with the greater basicity of the halide anions. The perturbed and shifted CH bending mode and its overtone were also observed, as well as perturbations to the CF stretching and bending modes. The spectral evidence tentatively suggests a monodentate hydrogen bond for the (CF 2H) 2O•F - complex, rather than the bidentate structure inferred from ion cyclotron resonance data.

  10. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 1 covers papers on the advances of gas phase ion chemistry. The book discusses the advances in flow tubes and the measurement of ion-molecule rate coefficients and product distributions; the ion chemistry of the earth's atmosphere; and the classical ion-molecule collision theory. The text also describes statistical methods in reaction dynamics; the state selection by photoion-photoelectron coincidence; and the effects of temperature and pressure in the kinetics of ion-molecule reactions. The energy distribution in the unimolecular decomposition of ions, as well

  11. Copper-Catalyzed Redox-Triggered Remote C-H Functionalization: Highly Selective Formation of C-CF3 and C-O Bonds

    Institute of Scientific and Technical Information of China (English)

    Taotao Li; Peng Yu; Jin-Shun Lin; Yonggang Zhi; Xin-Yuan Liu

    2016-01-01

    A Cu-catalyzed remote sp3 C-H/unactivated alkenes functionalization reaction for the concomitant construction ofC-CF3 and C-O bonds was described.An 1,5-H radical transfer involving an sp3 C-H bond adjacent to a nitrogen atom and an α-CF3-alkyl radical intermediate derived from unactivated alkenes was observed and demonstrated to proceed via the radical process.

  12. Basic Chemistry for the Cement Industry.

    Science.gov (United States)

    Turner, Mason

    This combined student workbook and instructor's guide contains nine units for inplant classes on basic chemistry for employees in the cement industry. The nine units cover the following topics: chemical basics; measurement; history of cement; atoms; bonding and chemical formulas; solids, liquids, and gases; chemistry of Portland cement…

  13. HYDROGEN BONDING IN POLYMERIC ADSORBENTS BASED ADSORPTION AND SEPARATION

    Institute of Scientific and Technical Information of China (English)

    XUMancai; SHIZuoqing; 等

    2000-01-01

    After a concise introduction of hydrogen bonding effects in solute-solute and solute-solvent bonding,the design of polymeric adsorbents based on hydrogen bonding ,selectivity in adsorption through hydrogen bonding,and characterization of hydrogen bonding in adsorption and separation were reviewed with 28 references.

  14. Dynamic combinatorial libraries : new opportunities in systems chemistry

    NARCIS (Netherlands)

    Hunt, Rosemary A. R.; Otto, Sijbren; Hunt, Rosemary A.R.

    2011-01-01

    Combinatorial chemistry is a tool for selecting molecules with special properties. Dynamic combinatorial chemistry started off aiming to be just that. However, unlike ordinary combinatorial chemistry, the interconnectedness of dynamic libraries gives them an extra dimension. An understanding of thes

  15. Ultrafast laser control of vibrational dynamics for a two-dimensional model of HONO 2 in the ground electronic state: separation of conformers, control of the bond length, selective preparation of the discrete and the continuum states

    Science.gov (United States)

    Oppel, M.; Paramonov, G. K.

    1998-06-01

    Selective excitation of the vibrational bound and the continuum states, controlled by subpicosecond infrared (IR) laser pulses, is simulated within the Schrödinger wave function formalism for a two-dimensional model of the HONO 2 molecule in the ground electronic state. State-selective excitation of the OH bond is achieved by single optimal laser pulses, with the probability being 97% for the bound states and more than 91% for the resonances. Stable, long-living continuum states are prepared with more than 96% probability by two optimal laser pulses, with the expectation energy of the molecule being well above the dissociation threshold of the ON single bond, and its life-time being at least 100 ps. The length of the ON single bond can be controlled selectively: stretching and contraction by about 45% of its equilibrium length are demonstrated. Laser separation of spatial conformers of HONO 2 in inhomogeneous conditions occurring on an anisotropic surface or created by a direct current (DC) electric field is analysed. The relative yields of target conformers may be very high, ranging from 10 to 10 8, and the absolute yields of up to 40% and more are calculated.

  16. Water-Chemistry Data for Selected Springs, Geysers, and Streams in Yellowstone National Park, Wyoming, 1999-2000

    Science.gov (United States)

    Ball, James W.; McCleskey, R. Blaine; Nordstrom, D. Kirk; Holloway, JoAnn M.; Verplanck, Philip L.; Sturtevant, Sabin A.

    2002-01-01

    Sixty-seven water analyses are reported for samples collected from 44 hot springs and their overflow drainages and two ambient-temperature acid streams in Yellowstone National Park (YNP) during 1990-2000. Thirty-seven analyses are reported for 1999, 18 for June of 2000, and 12 for September of 2000. These water samples were collected and analyzed as part of research investigations in YNP on microbially mediated sulfur oxidation in stream water, arsenic and sulfur redox speciation in hot springs, and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. Most samples were collected from sources in the Norris Geyser Basin. Two ambient-temperature acidic stream systems, Alluvium and Columbine Creeks and their tributaries in Brimstone Basin, were studied in detail. Analyses were performed at or near the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability of the constituent and whether or not it could be preserved effectively. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity, acidity, and F were determined within a few days of sample collection by titration with acid, titration with base, and ion-selective electrode or ion chromatography (IC), respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by IC. Concentrations of Br, Cl, NH4, NO2, NO3, SO4, Fe(II), and Fe(total) were determined within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li and K were determined by flame atomic absorption spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), K, Li, Mg, Mn, Na, Ni, Pb, Se, Si, Sr, V, and Zn were determined by inductively-coupled plasma-optical emission spectrometry. Trace concentrations of Cd, Cr, Cu, Pb, and Sb were

  17. Geologic, water-chemistry, and hydrologic data from multiple-well monitoring sites and selected water-supply wells in the Santa Clara Valley, California, 1999-2003

    Science.gov (United States)

    Newhouse, M.W.; Hanson, R.T.; Wentworth, C.M.; Everett, Rhett; Williams, C.F.; Tinsley, J.C.; Noce, T.E.; Carkin, B.A.

    2004-01-01

    core samples indicate an average primary-wave velocity of about 5,515 feet per second, a bimodal distribution of density between 2.19 and 2.32 grams per cubic centimeter with an average of 2.16 grams per cubic centimeter, and a magnetic susceptibility that generally ranged between 9 and 40 with an average of 22. Water-chemistry data indicate that the ground water in the alluvial aquifers generally is low in total dissolved solids and chloride and of good quality. Isotopic data indicate that water from artificial recharge is present throughout the shallower parts of the aquifer system but may not be present toward the center of the valley. The percentage of water from artificial recharge present in ground water ranges from 0 to 61 percent for water-supply wells. The age of most shallow ground water is less than 2,000 years before present, and the age of deeper ground water is as much as 39,900 years before present, as determined from carbon age dates. Initial water-level data from the multiple-well monitoring sites indicate seasonal water-level fluctuations as great as 60 feet and water-level differences between aquifers as great as 10 feet. The water-level hydrographs indicate different water-level changes and relations between aquifers in different parts of the basin. However, most of these hydrographs indicate the potential for downward water-level gradients, with lower hydraulic heads in the deeper monitoring wells. Hydraulic properties of selected new monitoring wells indicate that horizontal hydraulic conductivities range from 0.1 to 583 feet per day. Hydraulic testing of selected core samples yielded vertical hydraulic conductivity values ranging from 8 x 10-4 to 0.3 feet per day, and effective porosity values ranging from 0.21 to 0.4. Geomechanical properties estimated from one-dimensional consolidation tests of selected core samples resulted in geometric mean inelastic and elastic specific storage values of 1.5 x 10-

  18. Bioinorganic Chemistry

    OpenAIRE

    Bertini, Ivano; Gray, Harry B.; Lippard, Stephen J.; Valentine, Joan Selverstone

    1994-01-01

    This book covers material that could be included in a one-quarter or one-semester course in bioinorganic chemistry for graduate students and advanced undergraduate students in chemistry or biochemistry. We believe that such a course should provide students with the background required to follow the research literature in the field. The topics were chosen to represent those areas of bioinorganic chemistry that are mature enough for textbook presentation. Although each chapter presents material...

  19. Social Chemistry

    OpenAIRE

    Lichtfouse, Eric; Schwarzbauer, Jan; Robert, Didier

    2012-01-01

    International audience This article is both an essay to propose social chemistry as a new scientific discipline, and a preface of the book Environmental Chemistry for a Sustainable World. Environmental chemistry is a fast emerging discipline aiming at the understanding the fate of pollutants in ecosystems and at designing novel processes that are safe for ecosystems. Past pollution should be cleaned, future pollution should be predicted and avoided (Lichtfouse et al., 2005a). Such advices ...

  20. Computational chemistry

    OpenAIRE

    Truhlar, Donald G.; McKoy, Vincent

    2000-01-01

    Computational chemistry has come of age. With significant strides in computer hardware and software over the last few decades, computational chemistry has achieved full partnership with theory and experiment as a tool for understanding and predicting the behavior of a broad range of chemical, physical, and biological phenomena. The Nobel Prize award to John Pople and Walter Kohn in 1998 highlighted the importance of these advances in computational chemistry. With massively parallel computers ...

  1. Problems in structural inorganic chemistry

    CERN Document Server

    Li, Wai-Kee; Mak, Thomas Chung Wai; Mak, Kendrew Kin Wah

    2013-01-01

    This book consists of over 300 problems (and their solutions) in structural inorganic chemistry at the senior undergraduate and beginning graduate level. The topics covered comprise Atomic and Molecular Electronic States, Atomic Orbitals, Hybrid Orbitals, Molecular Symmetry, Molecular Geometry and Bonding, Crystal Field Theory, Molecular Orbital Theory, Vibrational Spectroscopy, and Crystal Structure. The central theme running through these topics is symmetry, molecular or crystalline. The problems collected in this volume originate in examination papers and take-home assignments that have been part of the teaching of the book's two senior authors' at The Chinese University of Hong Kong over the past four decades. The authors' courses include Chemical Bonding, Elementary Quantum Chemistry, Advanced Inorganic Chemistry, X-Ray Crystallography, etc. The problems have been tested by generations of students taking these courses.

  2. Diffusion bonding

    Science.gov (United States)

    Anderson, Robert C.

    1976-06-22

    1. A method for joining beryllium to beryllium by diffusion bonding, comprising the steps of coating at least one surface portion of at least two beryllium pieces with nickel, positioning a coated surface portion in a contiguous relationship with an other surface portion, subjecting the contiguously disposed surface portions to an environment having an atmosphere at a pressure lower than ambient pressure, applying a force upon the beryllium pieces for causing the contiguous surface portions to abut against each other, heating the contiguous surface portions to a maximum temperature less than the melting temperature of the beryllium, substantially uniformly decreasing the applied force while increasing the temperature after attaining a temperature substantially above room temperature, and maintaining a portion of the applied force at a temperature corresponding to about maximum temperature for a duration sufficient to effect the diffusion bond between the contiguous surface portions.

  3. The Effects of the Property Tax Extension Limitation Law upon Revenue Growth, Bonded Debt, and School Business Leader Perceptions within Selected Illinois School Districts.

    Science.gov (United States)

    Hylbert, Danny

    2002-01-01

    Examines the effects of the Illinois Property Tax Extension Limitation Law on the revenue growth of collar counties and suburban school districts in Cook County. Finds that the law negatively affects revenue growth. Also finds, for example, that a majority of school business officials are motivated to increase their districts' bonded indebtedness.…

  4. Financial planning working capital ventures using software «analyzer bdds» sold on the basis of selection of optimal bond portfolio

    Directory of Open Access Journals (Sweden)

    N.J. Timofeeva

    2011-05-01

    Full Text Available This article examines the financial planning of working capital organizations, in particular presented a software implementation of the algorithm analyzes the budget forecast working capital, identify and take advantage of temporarily free money using a model of a decision on the choice of the optimal bond portfolio, consistent with the free flow of liquidity of the enterprise.

  5. Migration chemistry

    International Nuclear Information System (INIS)

    Migration chemistry, the influence of chemical -, biochemical - and physico-chemical reactions on the migration behaviour of pollutants in the environment, is an interplay between the actual natur of the pollutant and the characteristics of the environment, such as pH, redox conditions and organic matter content. The wide selection of possible pollutants in combination with varying geological media, as well as the operation of different chemical -, biochemical - and physico-chemical reactions compleactes the prediction of the influence of these processes on the mobility of pollutants. The report summarizes a wide range of potential pollutants in the terrestrial environment as well as a variety of chemical -, biochemical - and physico-chemical reactions, which can be expected to influence the migration behaviour, comprising diffusion, dispersion, convection, sorption/desorption, precipitation/dissolution, transformations/degradations, biochemical reactions and complex formation. The latter comprises the complexation of metal ions as well as non-polar organics to naturally occurring organic macromolecules. The influence of the single types of processes on the migration process is elucidated based on theoretical studies. The influence of chemical -, biochemical - and physico-chemical reactions on the migration behaviour is unambiguous, as the processes apparently control the transport of pollutants in the terrestrial environment. As the simple, conventional KD concept breaks down, it is suggested that the migration process should be described in terms of the alternative concepts chemical dispersion, average-elution-time and effective retention. (AB) (134 refs.)

  6. The correlation theory of the chemical bond

    CERN Document Server

    Szalay, Szilárd; Szilvási, Tibor; Veis, Libor; Legeza, Örs

    2016-01-01

    The notion of chemical bond is a very useful concept in chemistry. It originated at the beginning of chemistry, it is expressive for the classically thinking mind, and the errors arising from the approximative nature of the concept can often be ignored. In the first half of the twentieth century, however, we learned that the proper description of the microworld is given by quantum mechanics. Quantum mechanics gives more accurate results for chemical systems than any preceding model, however, it is very inexpressive for the classically thinking mind. The quantum mechanical description of the chemical bond is given in terms of delocalized bonding orbitals, or, alternatively, in terms of correlations of occupations of localized orbitals. However, in the latter case, multiorbital correlations were treated only in terms of two-orbital correlations, although the structure of multiorbital correlations is far richer; and, in the case of bonds established by more than two electrons, multiorbital correlations represent...

  7. 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

  8. Good chemistry

    OpenAIRE

    Petsko, Gregory A

    2004-01-01

    The subject matter in chemistry courses reflects almost nothing of the issues that chemists are interested in. It is important to formulate a set of topics - and a Medical College Admissions Test reflecting them - that would leave chemistry departments no choice but to change their teaching.

  9. Selective recovery of pure copper nanopowder from indium-tin-oxide etching wastewater by various wet chemical reduction process: Understanding their chemistry and comparisons of sustainable valorization processes.

    Science.gov (United States)

    Swain, Basudev; Mishra, Chinmayee; Hong, Hyun Seon; Cho, Sung-Soo

    2016-05-01

    Sustainable valorization processes for selective recovery of pure copper nanopowder from Indium-Tin-Oxide (ITO) etching wastewater by various wet chemical reduction processes, their chemistry has been investigated and compared. After the indium recovery by solvent extraction from ITO etching wastewater, the same is also an environmental challenge, needs to be treated before disposal. After the indium recovery, ITO etching wastewater contains 6.11kg/m(3) of copper and 1.35kg/m(3) of aluminum, pH of the solution is very low converging to 0 and contain a significant amount of chlorine in the media. In this study, pure copper nanopowder was recovered using various reducing reagents by wet chemical reduction and characterized. Different reducing agents like a metallic, an inorganic acid and an organic acid were used to understand reduction behavior of copper in the presence of aluminum in a strong chloride medium of the ITO etching wastewater. The effect of a polymer surfactant Polyvinylpyrrolidone (PVP), which was included to prevent aggregation, to provide dispersion stability and control the size of copper nanopowder was investigated and compared. The developed copper nanopowder recovery techniques are techno-economical feasible processes for commercial production of copper nanopowder in the range of 100-500nm size from the reported facilities through a one-pot synthesis. By all the process reported pure copper nanopowder can be recovered with>99% efficiency. After the copper recovery, copper concentration in the wastewater reduced to acceptable limit recommended by WHO for wastewater disposal. The process is not only beneficial for recycling of copper, but also helps to address environment challenged posed by ITO etching wastewater. From a complex wastewater, synthesis of pure copper nanopowder using various wet chemical reduction route and their comparison is the novelty of this recovery process. PMID:26918838

  10. Selective recovery of pure copper nanopowder from indium-tin-oxide etching wastewater by various wet chemical reduction process: Understanding their chemistry and comparisons of sustainable valorization processes.

    Science.gov (United States)

    Swain, Basudev; Mishra, Chinmayee; Hong, Hyun Seon; Cho, Sung-Soo

    2016-05-01

    Sustainable valorization processes for selective recovery of pure copper nanopowder from Indium-Tin-Oxide (ITO) etching wastewater by various wet chemical reduction processes, their chemistry has been investigated and compared. After the indium recovery by solvent extraction from ITO etching wastewater, the same is also an environmental challenge, needs to be treated before disposal. After the indium recovery, ITO etching wastewater contains 6.11kg/m(3) of copper and 1.35kg/m(3) of aluminum, pH of the solution is very low converging to 0 and contain a significant amount of chlorine in the media. In this study, pure copper nanopowder was recovered using various reducing reagents by wet chemical reduction and characterized. Different reducing agents like a metallic, an inorganic acid and an organic acid were used to understand reduction behavior of copper in the presence of aluminum in a strong chloride medium of the ITO etching wastewater. The effect of a polymer surfactant Polyvinylpyrrolidone (PVP), which was included to prevent aggregation, to provide dispersion stability and control the size of copper nanopowder was investigated and compared. The developed copper nanopowder recovery techniques are techno-economical feasible processes for commercial production of copper nanopowder in the range of 100-500nm size from the reported facilities through a one-pot synthesis. By all the process reported pure copper nanopowder can be recovered with>99% efficiency. After the copper recovery, copper concentration in the wastewater reduced to acceptable limit recommended by WHO for wastewater disposal. The process is not only beneficial for recycling of copper, but also helps to address environment challenged posed by ITO etching wastewater. From a complex wastewater, synthesis of pure copper nanopowder using various wet chemical reduction route and their comparison is the novelty of this recovery process.

  11. Carbohydrates in Supramolecular Chemistry.

    Science.gov (United States)

    Delbianco, Martina; Bharate, Priya; Varela-Aramburu, Silvia; Seeberger, Peter H

    2016-02-24

    Carbohydrates are involved in a variety of biological processes. The ability of sugars to form a large number of hydrogen bonds has made them important components for supramolecular chemistry. We discuss recent advances in the use of carbohydrates in supramolecular chemistry and reveal that carbohydrates are useful building blocks for the stabilization of complex architectures. Systems are presented according to the scaffold that supports the glyco-conjugate: organic macrocycles, dendrimers, nanomaterials, and polymers are considered. Glyco-conjugates can form host-guest complexes, and can self-assemble by using carbohydrate-carbohydrate interactions and other weak interactions such as π-π interactions. Finally, complex supramolecular architectures based on carbohydrate-protein interactions are discussed. PMID:26702928

  12. Electronic structure of selected thiazydes by means of {sup 35}Cl NQR and quantum chemistry calculation methods; Struktura elektronowa wybranych tiazydow badana metoda {sup 35}Cl - NQR oraz metodami obliczeniowymi chemii kwantowej

    Energy Technology Data Exchange (ETDEWEB)

    Latosinska, J.N.; Kasprzak, J.; Mazurek, P.; Nogaj, B. [Inst. Fizyki, Univ. A. Mickiewicza, (Poland); Latosinska, M. [Politechnika Poznanska, Poznan (Poland)

    1995-12-31

    The {sup 35}Cl NQR as well as MNDO and INDO quantum chemistry calculation methods have been used for determination of electronic structure of selected benzo ditiazine derivatives. The most probable molecular conformation has been taken into account. Also molecular dynamics has been studied for hydro chloro thiazole. The resonant frequency temperature dependence has been measured in the range of 77 - 300 K. 7 refs, 6 figs, 3 tabs.

  13. Quantum chemistry

    CERN Document Server

    Lowe, John P

    1993-01-01

    Praised for its appealing writing style and clear pedagogy, Lowe's Quantum Chemistry is now available in its Second Edition as a text for senior undergraduate- and graduate-level chemistry students. The book assumes little mathematical or physical sophistication and emphasizes an understanding of the techniques and results of quantum chemistry, thus enabling students to comprehend much of the current chemical literature in which quantum chemical methods or concepts are used as tools. The book begins with a six-chapter introduction of standard one-dimensional systems, the hydrogen atom,

  14. Exploring Conceptual Frameworks of Models of Atomic Structures and Periodic Variations, Chemical Bonding, and Molecular Shape and Polarity: A Comparison of Undergraduate General Chemistry Students with High and Low Levels of Content Knowledge

    Science.gov (United States)

    Wang, Chia-Yu; Barrow, Lloyd H.

    2013-01-01

    The purpose of the study was to explore students' conceptual frameworks of models of atomic structure and periodic variations, chemical bonding, and molecular shape and polarity, and how these conceptual frameworks influence their quality of explanations and ability to shift among chemical representations. This study employed a purposeful sampling…

  15. The chemistry of silicon

    CERN Document Server

    Rochow, E G; Emeléus, H J; Nyholm, Ronald

    1975-01-01

    Pergamon Texts in Organic Chemistry, Volume 9: The Chemistry of Silicon presents information essential in understanding the chemical properties of silicon. The book first covers the fundamental aspects of silicon, such as its nuclear, physical, and chemical properties. The text also details the history of silicon, its occurrence and distribution, and applications. Next, the selection enumerates the compounds and complexes of silicon, along with organosilicon compounds. The text will be of great interest to chemists and chemical engineers. Other researchers working on research study involving s

  16. Chemistry in microelectronics

    CERN Document Server

    Le Tiec, Yannick

    2013-01-01

    Microelectronics is a complex world where many sciences need to collaborate to create nano-objects: we need expertise in electronics, microelectronics, physics, optics and mechanics also crossing into chemistry, electrochemistry, as well as biology, biochemistry and medicine. Chemistry is involved in many fields from materials, chemicals, gases, liquids or salts, the basics of reactions and equilibrium, to the optimized cleaning of surfaces and selective etching of specific layers. In addition, over recent decades, the size of the transistors has been drastically reduced while the functionalit

  17. Materials Chemistry

    CERN Document Server

    Fahlman, Bradley D

    2011-01-01

    The 2nd edition of Materials Chemistry builds on the strengths that were recognized by a 2008 Textbook Excellence Award from the Text and Academic Authors Association (TAA). Materials Chemistry addresses inorganic-, organic-, and nano-based materials from a structure vs. property treatment, providing a suitable breadth and depth coverage of the rapidly evolving materials field. The 2nd edition continues to offer innovative coverage and practical perspective throughout. After briefly defining materials chemistry and its history, seven chapters discuss solid-state chemistry, metals, semiconducting materials, organic "soft" materials, nanomaterials, and materials characterization. All chapters have been thoroughly updated and expanded with, for example, new sections on ‘soft lithographic’ patterning, ‘click chemistry’ polymerization, nanotoxicity, graphene, as well as many biomaterials applications. The polymer and ‘soft’ materials chapter represents the largest expansion for the 2nd edition. Each ch...

  18. Introductory Chemistry

    OpenAIRE

    Baron, Mark; Gonzalez-Rodriguez, Jose; Stevens, Gary; Gray, Nathan; Atherton, Thomas; Winn, Joss

    2010-01-01

    Teaching and Learning resources for the 1st Year Introductory Chemistry course (Forensic Science). 30 credits. These are Open Educational Resources (OER), made available for re-use under a Creative Commons license.

  19. Analytical chemistry

    International Nuclear Information System (INIS)

    This book is comprised of nineteen chapters, which describes introduction of analytical chemistry, experimental error and statistics, chemistry equilibrium and solubility, gravimetric analysis with mechanism of precipitation, range and calculation of the result, volume analysis on general principle, sedimentation method on types and titration curve, acid base balance, acid base titration curve, complex and firing reaction, introduction of chemical electro analysis, acid-base titration curve, electrode and potentiometry, electrolysis and conductometry, voltammetry and polarographic spectrophotometry, atomic spectrometry, solvent extraction, chromatograph and experiments.

  20. Green Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Collison, Melanie

    2011-05-15

    Green chemistry is the science of chemistry used in a way that will not use or create hazardous substances. Dr. Rui Resendes is working in this field at GreenCentre Canada, an offshoot of PARTEQ Innovations in Kingston, Ontario. GreenCentre's preliminary findings suggest their licensed product {sup S}witchable Solutions{sup ,} featuring 3 classes of solvents and a surfactant, may be useful in bitumen oil sands extraction.

  1. Cluster Chemistry

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    @@ Cansisting of eight scientists from the State Key Laboratory of Physical Chemistry of Solid Surfaces and Xiamen University, this creative research group is devoted to the research of cluster chemistry and creation of nanomaterials.After three-year hard work, the group scored a series of encouraging progresses in synthesis of clusters with special structures, including novel fullerenes, fullerene-like metal cluster compounds as well as other related nanomaterials, and their properties study.

  2. Formation of Self-Templated 2,6-Bis(1,2,3-triazol-4-yl)pyridine [2]Catenanes by Triazolyl Hydrogen Bonding: Selective Anion Hosts for Phosphate.

    Science.gov (United States)

    Byrne, Joseph P; Blasco, Salvador; Aletti, Anna B; Hessman, Gary; Gunnlaugsson, Thorfinnur

    2016-07-25

    We report the remarkable ability of 2,6-bis(1,2,3-triazol-4-yl)pyridine (btp) compounds 2 with appended olefin amide arms to self-template the formation of interlocked [2]catenane structures 3 in up to 50 % yield when subjected to olefin ring-closing metathesis in CH2 Cl2 . X-ray diffraction crystallography enabled the structural characterization of both the [2]catenane 3 a and the non-interlocked macrocycle 4 a. These [2]catenanes showed selective triazolyl hydrogen-bonding interactions with the tetrahedral phosphate anion when screened against a range of ions; 3 a,b are the first examples of selective [2]catenane hosts for phosphate. PMID:27295556

  3. Principles of Chemistry (by Michael Munowitz)

    Science.gov (United States)

    Kovac, Reviewed By Jeffrey

    2000-05-01

    At a time when almost all general chemistry textbooks seem to have become commodities designed by marketing departments to offend no one, it is refreshing to find a book with a unique perspective. Michael Munowitz has written what I can only describe as a delightful chemistry book, full of conceptual insight, that uses a novel and interesting pedagogic strategy. This is a book that has much to recommend it. This is the best-written general chemistry book I have ever read. An editor with whom I have worked recently remarked that he felt his job was to help authors make their writing sing. Well, the writing in Principles of Chemistry sings with the full, rich harmonies and creative inventiveness of the King's Singers or Chanticleer. Here is the first sentence of the introduction: "Central to any understanding of the physical world is one discovery of paramount importance, a truth disarmingly simple yet profound in its implications: matter is not continuous." This is prose to be savored and celebrated. Principles of Chemistry has a distinct perspective on chemistry: the perspective of the physical chemist. The focus is on simplicity, what is common about molecules and reactions; begin with the microscopic and build bridges to the macroscopic. The author's perspective is clear from the organization of the book. After three rather broad introductory chapters, there are four chapters that develop the quantum mechanical theory of atoms and molecules, including a strong treatment of molecular orbital theory. Unlike many books, Principles of Chemistry presents the molecular orbital approach first and introduces valence bond theory later only as an approximation for dealing with more complicated molecules. The usual chapters on descriptive inorganic chemistry are absent (though there is an excellent chapter on organic and biological molecules and reactions as well as one on transition metal complexes). Instead, descriptive chemistry is integrated into the development of

  4. Recent progress in actinide borate chemistry.

    Science.gov (United States)

    Wang, Shuao; Alekseev, Evgeny V; Depmeier, Wulf; Albrecht-Schmitt, Thomas E

    2011-10-21

    The use of molten boric acid as a reactive flux for synthesizing actinide borates has been developed in the past two years providing access to a remarkable array of exotic materials with both unusual structures and unprecedented properties. [ThB(5)O(6)(OH)(6)][BO(OH)(2)]·2.5H(2)O possesses a cationic supertetrahedral structure and displays remarkable anion exchange properties with high selectivity for TcO(4)(-). Uranyl borates form noncentrosymmetric structures with extraordinarily rich topological relationships. Neptunium borates are often mixed-valent and yield rare examples of compounds with one metal in three different oxidation states. Plutonium borates display new coordination chemistry for trivalent actinides. Finally, americium borates show a dramatic departure from plutonium borates, and there are scant examples of families of actinides compounds that extend past plutonium to examine the bonding of later actinides. There are several grand challenges that this work addresses. The foremost of these challenges is the development of structure-property relationships in transuranium materials. A deep understanding of the materials chemistry of actinides will likely lead to the development of advanced waste forms for radionuclides present in nuclear waste that prevent their transport in the environment. This work may have also uncovered the solubility-limiting phases of actinides in some repositories, and allows for measurements on the stability of these materials. PMID:21915396

  5. Identification and cleavage of breakable single bonds by selective oxidation, reduction, and hydrolysis. Quarterly report No. 1, October 1-December 31, 1978

    Energy Technology Data Exchange (ETDEWEB)

    Buchanan, D.H.; Mayo, F.R.

    1979-01-25

    Bituminous coal is assumed to consist mostly of an aggregate of condensed aromatic and aliphatic rings, connected and made insoluble (but swellable) by crosslinks containing only single bonds. These connecting links consist mainly, possibly entirely, of combinations of carbon-carbon single bonds and ether (possibly ester) groups. It is at these crosslinks that the most extensive cuts can be made in the coal structure (to make it soluble or liquid) under the mildest conditions and with the least loss in fuel values. The objective of this project is to determine the proportion of the various kinds of connecting links and how they can best be broken; in other words, to determine the structure of coal with emphasis on the crosslinks. At present, our attention is directed to five kinds of connecting links: single (Ar-CH/sub 2/-Ar) and multiple methylene groups (Ar-(CH/sub 2/)/sub 2/-Ar) and three kinds of ethers, Ar-O-Ar, Ar-O-R, and R-O-R (Ar represents an aromatic aggregate and R is attached to O through at least one aliphatic carbon.) The work described in this quarterly report deals mainly with the oxidation of pyridine-extracted coal by O/sub 2/ and the cleavage by sodium in liquid ammonia of aromatic ether linkages in a pyridine-soluble, toluene-insoluble fraction of coal extract. Products from the NaOCl oxidation of pyridine-extracted coal were also studied by nuclear magnetic resonance (NMR) and acid-base titrations. 7 references, 2 figures, 6 tables.

  6. Radiation Chemistry

    Science.gov (United States)

    Wojnárovits, L.

    Ionizing radiation causes chemical changes in the molecules of the interacting medium. The initial molecules change to new molecules, resulting in changes of the physical, chemical, and eventually biological properties of the material. For instance, water decomposes to its elements H2 and O2. In polymers, degradation and crosslinking take place. In biopolymers, e.g., DNS strand breaks and other alterations occur. Such changes are to be avoided in some cases (radiation protection), however, in other cases they are used for technological purposes (radiation processing). This chapter introduces radiation chemistry by discussing the sources of ionizing radiation (radionuclide sources, machine sources), absorption of radiation energy, techniques used in radiation chemistry research, and methods of absorbed energy (absorbed dose) measurements. Radiation chemistry of different classes of inorganic (water and aqueous solutions, inorganic solids, ionic liquids (ILs)) and organic substances (hydrocarbons, halogenated compounds, polymers, and biomolecules) is discussed in concise form together with theoretical and experimental backgrounds. An essential part of the chapter is the introduction of radiation processing technologies in the fields of polymer chemistry, food processing, and sterilization. The application of radiation chemistry to nuclear technology and to protection of environment (flue gas treatment, wastewater treatment) is also discussed.

  7. Direct bonded space maintainers.

    Science.gov (United States)

    Santos, V L; Almeida, M A; Mello, H S; Keith, O

    1993-01-01

    The aim of this study was to evaluate clinically a bonded space maintainer, which would reduce chair-side time and cost. Sixty appliances were fabricated from 0.7 mm stainless steel round wire and bonded using light-cured composite to the two teeth adjacent to the site of extraction of a posterior primary tooth. Twenty males and sixteen females (age range 5-9-years-old) were selected from the Pedodontic clinic of the State University of Rio de Janeiro. The sixty space maintainers were divided into two groups according to the site in which they were placed: a) absent first primary molar and b) absent second primary molar. Impressions and study models were obtained prior to and 6 months after bonding the appliances. During this period only 8.3% of failures were observed, most of them from occlusal or facial trauma. Student t-test did not show statistically significant alterations in the sizes of the maintained spaces during the trial period.

  8. Facile scission of isonitrile carbon–nitrogen triple bond using a diborane(4) reagent

    OpenAIRE

    Asakawa, Hiroki; Lee, Ka-Ho; Lin, Zhenyang; Yamashita, Makoto

    2014-01-01

    Transition metal reagents and catalysts are generally effective to cleave all three bonds (one σ and two π) in a triple bond despite its high bonding energy. Recently, chemistry of single-bond cleavage by using main-group element compounds is rapidly being developed in the absence of transition metals. However, the cleavage of a triple bond using non-transition-metal compounds is less explored. Here we report that an unsymmetrical diborane(4) compound could react with carbon monoxide and tert...

  9. Bonds and bands in semiconductors

    CERN Document Server

    Phillips, Jim

    2009-01-01

    This classic work on the basic chemistry and solid state physics of semiconducting materials is now updated and improved with new chapters on crystalline and amorphous semiconductors. Written by two of the world's pioneering materials scientists in the development of semiconductors, this work offers in a single-volume an authoritative treatment for the learning and understanding of what makes perhaps the world's most important engineered materials actually work. Readers will find: --' The essential principles of chemical bonding, electron energy bands and their relationship to conductive and s

  10. Polymer Chemistry

    Science.gov (United States)

    Williams, Martha; Roberson, Luke; Caraccio, Anne

    2010-01-01

    This viewgraph presentation describes new technologies in polymer and material chemistry that benefits NASA programs and missions. The topics include: 1) What are Polymers?; 2) History of Polymer Chemistry; 3) Composites/Materials Development at KSC; 4) Why Wiring; 5) Next Generation Wiring Materials; 6) Wire System Materials and Integration; 7) Self-Healing Wire Repair; 8) Smart Wiring Summary; 9) Fire and Polymers; 10) Aerogel Technology; 11) Aerogel Composites; 12) Aerogels for Oil Remediation; 13) KSC's Solution; 14) Chemochromic Hydrogen Sensors; 15) STS-130 and 131 Operations; 16) HyperPigment; 17) Antimicrobial Materials; 18) Conductive Inks Formulations for Multiple Applications; and 19) Testing and Processing Equipment.

  11. Recommendations of the American Chemical Society Chemistry Education Task Force.

    Science.gov (United States)

    Yankwich, Peter E.; And Others

    1984-01-01

    Presents selected recommendations from the American Chemical Society Chemistry Education Task Force's list of 39 principal and 52 supplementary recommendations. Those listed focus on all levels of education, elementary school science, high school chemistry and science, two-year college chemistry, college/university chemistry and science, chemistry…

  12. To Bond or Not to Bond? That Is the Question

    Science.gov (United States)

    Balzer, Wayne E.

    2015-01-01

    This case, inspired by a real school district scenario, was developed for use in a graduate-level course in school finance. James Spencer had just been selected as the new superintendent of a low-income, 400-student, rural school district in need of many capital improvements. The previous superintendent had refused to hold a bond election because…

  13. The Kjeldahl method as a primary reference procedure for total protein in certified reference materials used in clinical chemistry. II. Selection of direct Kjeldahl analysis and its preliminary performance parameters.

    Science.gov (United States)

    Vinklárková, Bára; Chromý, Vratislav; Šprongl, Luděk; Bittová, Miroslava; Rikanová, Milena; Ohnútková, Ivana; Žaludová, Lenka

    2015-01-01

    To select a Kjeldahl procedure suitable for the determination of total protein in reference materials used in laboratory medicine, we reviewed in our previous article Kjeldahl methods adopted by clinical chemistry and found an indirect two-step analysis by total Kjeldahl nitrogen corrected for its nonprotein nitrogen and a direct analysis made on isolated protein precipitates. In this article, we compare both procedures on various reference materials. An indirect Kjeldahl method gave falsely lower results than a direct analysis. Preliminary performance parameters qualify the direct Kjeldahl analysis as a suitable primary reference procedure for the certification of total protein in reference laboratories.

  14. Organic chemistry

    International Nuclear Information System (INIS)

    The activities of the mycotoxin research group are discussed. This includes the isolation and structure determination of mycotoxins, plant products, the biosyntheris of mycotoxins, the synthesis and characteristics of steroids, the synthesis and mechanistic aspects of heterocyclic chemistry and the functionality of steroids over long distances. Nmr spectra and mass spectroscopy are some of the techniques used

  15. Reinventing Chemistry

    OpenAIRE

    Whitesides, George McClelland

    2015-01-01

    Chemistry is in a period of change, from an era focused on molecules and reactions, to one in which manipulations of systems of molecules and reactions will be essential parts of controlling larger systems. This Essay traces paths from the past to possible futures.

  16. Cross Shear Roll Bonding

    DEFF Research Database (Denmark)

    Bay, Niels; Bjerregaard, Henrik; Petersen, Søren. B;

    1994-01-01

    The present paper describes an investigation of roll bonding an AlZn alloy to mild steel. Application of cross shear roll bonding, where the two equal sized rolls run with different peripheral speed, is shown to give better bond strength than conventional roll bonding. Improvements of up to 20......-23% in bond strength are found and full bond strength is obtained at a reduction of 50% whereas 65% is required in case of conventional roll bonding. Pseudo cross shear roll bonding, where the cross shear effect is obtained by running two equal sized rolls with different speed, gives the same results....

  17. Green chemistry: development trajectory

    Science.gov (United States)

    Moiseev, I. I.

    2013-07-01

    Examples of applications of green chemistry methods in heavy organic synthesis are analyzed. Compounds, which can be produced by the processing of the biomass, and the criteria for the selection of the most promising products are summarized. The current status of the ethanol production and processing is considered. The possibilities of the use of high fatty acid triglycerides, glycerol, succinic acid, and isoprene are briefly discussed. The bibliography includes 67 references.

  18. Abstracts of the 2. Brazilian Symposium on Theoretical Chemistry

    International Nuclear Information System (INIS)

    Abstracts from research works on theoretical chemistry are presented. Main subjects of study are: metallic bonds, hyperfine interactions, symetry of isotopically substituted molecules, photoionization reactions, electron impact reactions, applications of the perturbation theory. (C.L.B.)

  19. C8-Selective Acylation of Quinoline N-Oxides with α-Oxocarboxylic Acids via Palladium-Catalyzed Regioselective C-H Bond Activation.

    Science.gov (United States)

    Chen, Xiaopei; Cui, Xiuling; Wu, Yangjie

    2016-08-01

    A facile and efficient protocol for palladium-catalyzed C8-selective acylation of quinoline N-oxides with α-oxocarboxylic acids has been developed. In this approach, N-oxide was utilized as a stepping stone for the remote C-H functionalization. The reactions proceeded efficiently under mild reaction conditions with excellent regioselectivity and broad functional group tolerance. PMID:27441527

  20. Catalysis and sustainable (green) chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Centi, Gabriele; Perathoner, Siglinda [Dipartimento di Chimica Industriale ed Ingegneria dei Materiali, University of Messina, Salita Sperone 31, 98166 Messina (Italy)

    2003-01-15

    Catalysis is a key technology to achieve the objectives of sustainable (green) chemistry. After introducing the concepts of sustainable (green) chemistry and a brief assessment of new sustainable chemical technologies, the relationship between catalysis and sustainable (green) chemistry is discussed and illustrated via an analysis of some selected and relevant examples. Emphasis is also given to the concept of catalytic technologies for scaling-down chemical processes, in order to develop sustainable production processes which reduce the impact on the environment to an acceptable level that allows self-depuration processes of the living environment.

  1. 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...

  2. Functionalization and bioimmobilization of silicon surfaces with Si–N bonded monolayer

    Energy Technology Data Exchange (ETDEWEB)

    Masood, Muhammad Nasir, E-mail: chemnasir_76@yahoo.com [Bios Lab on a Chip Group, MESA+ Institute for Nanotechnology, University of Twente, Enschede (Netherlands); Department of Physics and Applied Mathematics, Pakistan Institute of Engineering and Applied Sciences (PIEAS), Nilore, Islamabad (Pakistan); Carlen, Edwin T.; Berg, Albert van den [Bios Lab on a Chip Group, MESA+ Institute for Nanotechnology, University of Twente, Enschede (Netherlands)

    2015-05-15

    Highlights: • Chemistry of Ethylene diamine (EDA) studied by X-ray photoelectron spectroscopy (XPS) on hydrogen terminated Si (1 1 1) surface under UV-irradiation. • Fast, efficient and selective surface modification via symmetric functional molecule. • Do not involve protection and deprotection steps which deteoriate the monolayer integrity, time consuming and expensive. • Si–N bond remain intact on sub-oxidized silicon surface. • Free amine groups availability for bioimmobilization. • Selectivity and sensitivity was demonstrated by SEM, fluorscence and electrochemical (C–V) measurements. - Abstract: A new method for selective surface functionalization of silicon with a silicon–nitrogen bonded (Si–N) monolayer and subsequent bioimmobilization is presented. The Si–N monolayer was studied using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), fluorescence spectroscopy, and capacitance–voltage (C–V) measurements using an electrolyte insulator semiconductor (EIS) sensor. A symmetric ethylene diamine (EDA, C{sub 2}H{sub 4} (NH{sub 2}){sub 2}) molecule was used as a precursor compound for monolayer formation in an inert environment in the liquid phase. XPS results show the attachment of EDA molecules proceeds via dissociative and dative bond formation whereas free amine groups on the surface were used for further immobilization of biomolecules. SEM shows selective functionalization and bioimmobilization on a patterned surface such as a silicon nanowire on silicon oxide substrate. Biosensing experiments with bioimmobilized surfaces were carried out in aqueous buffer and show high sensitivity for biosensing.

  3. Selective separation of Am(III) from Eu(III) by 2,9-Bis(dialkyl-1,2,4-triazin-3-yl)-1,10-phenanthrolines. A relativistic quantum chemistry study

    Energy Technology Data Exchange (ETDEWEB)

    Xiao, Cheng-Liang; Wang, Cong-Zhi; Lan, Jian-Hui; Yuan, Li-Yong; Zhao, Yu-Liang; Shi, Wei-Qun [Chinese Academy of Sciences, Beijing (China). Key Lab. of Nuclear Radiation and Nuclear Energy Technology and Key Lab. for Biomedical Effects of Nanomaterials and Nanosafety; Chai, Zhi-Fang [Chinese Academy of Sciences, Beijing (China). Key Lab. of Nuclear Radiation and Nuclear Energy Technology and Key Lab. for Biomedical Effects of Nanomaterials and Nanosafety; Soochow Univ., Suzhou (China). School of Radiological and Interdisciplinary Sciences

    2014-07-01

    The complexation properties of Am(III) and Eu(III) with a serial of novel N-heterocyclic tetradentate ligands, 2,9-bis(dialkyl-1,2,4-triazin-3-yl)-1,10-phenanth-rolines (BTPhens), have been calculated by density functional theory (DFT) coupled with relativistic small-core pseudopotential. It is found that the nitrogen atoms in triazine rings favor metal cations more than those in phenanthroline skeleton. The Am-N bond lengths are comparable to or even shorter than those of Eu-N bonds based on the larger radii of Am(III) than Eu(III). The effect of alkyl substituents on the complex structures is limited but they can adjust the complexation reaction and extraction kinetics. Additionally, the solvent effect can decrease the probability of the complexation reactions greatly and the solvation energies of Am(III) and Eu(III) might be the primary driving force in the complexation selectivity. The complexation reactions for forming ML(NO{sub 3}){sub 3} and [ML{sub 2}(NO{sub 3})]{sup 2+} complexes are believed to dominate the selective extraction separation of Am(III) from Eu(III) in nitric acid media, which agrees well with the experimental results. The comparisons of BTPhens with BTBPs in dipoles and electronic structures confirm that the BTPhens exhibit more favourable extraction kinetics and selectivity for minor actinides.

  4. 选择性氧化形成三对二硫键合成齐考诺肽%Synthesis of Ziconotide by Selective Oxidation to Form Three Disulfide Bonds

    Institute of Scientific and Technical Information of China (English)

    曹本文; 王卫国; 李战雄; 徐红岩

    2011-01-01

    Using the different oxidation reactivity of sulfhydryls with different protective group, Ziconotide was synthesized via selective oxidation reaction. Firstly, two disulfide bonds were formatted between the 1,8,16,20-position sulfhydryls protected by Trt in the Ziconotide by air oxidation. Then,the third disulfide bond was formatted between the 15,25-position sulfhydryls protected by Acm with iodine oxidation.%利用不同保护基保护的巯基的氧化反应性不同,分别以空气和碘作为氧化剂,通过选择性氧化工艺使齐考诺肽线性肽的1,8,16,20-位两对Trt保护巯基先形成两对二硫键,然后用碘氧化15,25-位Acm保护的巯基,成功地生成第三对二硫键,合成了齐考诺肽.

  5. Nonthermal plasma chemistry and physics

    CERN Document Server

    Meichsner, Jurgen; Schneider, Ralf; Wagner, Hans-Erich

    2013-01-01

    In addition to introducing the basics of plasma physics, Nonthermal Plasma Chemistry and Physics is a comprehensive presentation of recent developments in the rapidly growing field of nonthermal plasma chemistry. The book offers a detailed discussion of the fundamentals of plasma chemical reactions and modeling, nonthermal plasma sources, relevant diagnostic techniques, and selected applications.Elucidating interconnections and trends, the book focuses on basic principles and illustrations across a broad field of applications. Expert contributors address environmental aspects of plasma chemist

  6. Direct carbon-carbon bond formation via reductive soft enolization: a syn-selective Mannich addition of α-iodo thioesters.

    Science.gov (United States)

    Truong, Ngoc; Sauer, Scott J; Seraphin-Hatcher, Cyndie; Coltart, Don M

    2016-08-16

    The β-amino carboxylic acid moiety is a key feature of numerous important biologically active compounds. We describe a syn-selective direct Mannich addition reaction that uses α-iodo thioesters and sulfonyl imines and produces β-amino thioesters. Enolate formation is achieved by reductive soft enolization. The products of the reaction provide straightforward access to biologically important β-lactams through a variety of known reactions. PMID:27492274

  7. Effect of pretreatment bias on the nucleation and growth mechanisms of ultrananocrystalline diamond films via bias-enhanced nucleation and growth: An approach to interfacial chemistry analysis via chemical bonding mapping

    International Nuclear Information System (INIS)

    The effect of pretreatment bias on the nucleation and growth mechanisms of the ultrananocrystalline diamond (UNCD) films on the Si substrate via bias-enhanced nucleation and bias-enhanced growth (BEN-BEG) was investigated using cross-sectional high-resolution transmission electron microscopy, chemical bonding mapping, and Raman spectroscopy. The mirror-polished substrate surface showed the formation of a triangular profile produced by a dominant physical sputtering mechanism induced by ion bombardment of ions from the hydrogen plasma accelerated toward the substrate due to biasing and a potential hydrogen-induced chemical reaction component before synthesizing the UNCD films. The BEN-BEG UNCD films grown on the Si substrate with biased and unbiased pretreatments in the hydrogen plasma were compared. In the case of the bias-pretreated substrate, the SiC phases were formed at the peaks of the Si surface triangular profile due to the active unsaturated Si bond and the enhanced local electrical field. The UNCD grains grew preferentially at the peaks of the triangular substrate surface profile and rapidly covered the amorphous carbon (a-C) and oriented graphite phases formed in the valley of the surface profile. In the case of the substrate with unbiased pretreatment, the SiC phases were formed via the reactions between the hydrocarbon species and the active Si atoms released from the substrate with assistance of the hydrogen plasma. The UNCD grains nucleated on the nucleating sites consisting of the SiC, a-C, and graphite phases. Growth mechanisms for the BEN-BEG UNCD films on both Si substrates were proposed to elucidate the different nucleation processes. Applying bias on the Si substrate pretreated in the hydrogen plasma optimized the nucleation sites for growth of UNCD grains, resulting in the low content of the nondiamond phases in UNCD films

  8. Advances in high temperature chemistry 1

    CERN Document Server

    Eyring, Leroy

    2013-01-01

    Advances in High Temperature Chemistry, Volume 1 describes the complexities and special and changing characteristics of high temperature chemistry. After providing a brief definition of high temperature chemistry, this nine-chapter book goes on describing the experiments and calculations of diatomic transition metal molecules, as well as the advances in applied wave mechanics that may contribute to an understanding of the bonding, structure, and spectra of the molecules of high temperature interest. The next chapter provides a summary of gaseous ternary compounds of the alkali metals used in

  9. Development of the Bonding Representations Inventory to Identify Student Misconceptions about Covalent and Ionic Bonding Representations

    Science.gov (United States)

    Luxford, Cynthia J.; Bretz, Stacey Lowery

    2014-01-01

    Teachers use multiple representations to communicate the concepts of bonding, including Lewis structures, formulas, space-filling models, and 3D manipulatives. As students learn to interpret these multiple representations, they may develop misconceptions that can create problems in further learning of chemistry. Interviews were conducted with 28…

  10. On Bond Portfolio Management

    OpenAIRE

    Vladislav Kargin

    2002-01-01

    This paper describes a new method of bond portfolio optimization based on stochastic string models of correlation structure in bond returns. The paper shows how to approximate correlation function of bond returns, compute the optimal portfolio allocation using Wiener-Hopf factorization, and check whether a collection of bonds presents arbitrage opportunities.

  11. Techniques for detecting effects of urban and rural land-use practices on stream-water chemistry in selected watersheds in Texas, Minnesota,and Illinois

    Science.gov (United States)

    Walker, J.F.

    1993-01-01

    Although considerable effort has been expended during the past two decades to control nonpoint-source contamination of streams and lakes in urban and rural watersheds, little has been published on the effectiveness of various management practices at the watershed scale. This report presents a discussion of several parametric and nonparametric statistical techniques for detecting changes in water-chemistry data. The need for reducing the influence of natural variability was recognized and accomplished through the use of regression equations. Traditional analyses have focused on fixed-frequency instantaneous concentration data; this report describes the use of storm load data as an alternative.

  12. Evaluation of the PC-SAFT, SAFT and CPA equations of state in predicting derivative properties of selected non-polar and hydrogen-bonding compounds

    DEFF Research Database (Denmark)

    de Villiers, A.J.; Schwarz, C.E.; Burger, A.J.;

    2013-01-01

    of these models to predict selected properties (heat capacities, pressure-volume derivative, pressure-temperature derivative and speed of sound) are evaluated for n-alkanes and 1-acohols. For n-alkanes, it is shown that the cubic term of CPA is unable to describe the pressure-volume derivative at high pressures...... are unable to accurately correlate the isochoric heat capacity, indicating an incorrect temperature dependency in these models. PC-SAFT shows peculiar behaviour in the description of the isobaric heat capacity of alkanes that can be traced back to the incorrect description of the pressure...

  13. Disk Chemistry*

    OpenAIRE

    Thi Wing-Fai

    2015-01-01

    The chemical species in protoplanetary disks react with each other. The chemical species control part of the thermal balance in those disks. How the chemistry proceeds in the varied conditions encountered in disks relies on detailed microscopic understanding of the reactions through experiments or theoretical studies. This chapter strives to summarize and explain in simple terms the different types of chemical reactions that can lead to complex species. The first part of the chapter deals wit...

  14. Interstellar chemistry

    OpenAIRE

    Klemperer, William

    2006-01-01

    In the past half century, radioastronomy has changed our perception and understanding of the universe. In this issue of PNAS, the molecular chemistry directly observed within the galaxy is discussed. For the most part, the description of the molecular transformations requires specific kinetic schemes rather than chemical thermodynamics. Ionization of the very abundant molecular hydrogen and atomic helium followed by their secondary reactions is discussed. The rich variety of organic species o...

  15. Dithioacetal Exchange: A New Reversible Reaction for Dynamic Combinatorial Chemistry.

    Science.gov (United States)

    Orrillo, A Gastón; Escalante, Andrea M; Furlan, Ricardo L E

    2016-05-10

    Reversibility of dithioacetal bond formation is reported under acidic mild conditions. Its utility for dynamic combinatorial chemistry was explored by combining it with orthogonal disulfide exchange. In such a setup, thiols are positioned at the intersection of both chemistries, constituting a connecting node between temporally separated networks.

  16. A selected ion flow tube investigation of the positive ion chemistry of a number of bromine containing fully and partially halogenated hydrocarbons

    International Nuclear Information System (INIS)

    The reaction of ions with neutral molecules play a significant, and often dominant, role in the chemistry of many gaseous plasma environments, including the interstellar medium, planetary ionospheres and industrial plasmas. This had led to many publications reporting ion-molecule reaction rate coefficients and reaction pathways (product ion distributions). Such critical data are invaluable in the understanding of the formation and abundance of ions and neutral molecules present in neutral and man-made plasma, and to predict how such plasmas chemically and physically evolve. There have been many studies investigating the positive ion chemistry of chlorofluorocarbons (CFCs), and a number of studies have explored the positive ion chemistry of their replacements, the perfluorocarbones (PFCs). In part these studies have been undertaken because of their relevance to plasmas, and of more specific interest in terms of their relevance to industrial plasma processing. Halogenated molecules are commonly used in plasma processes. In contrast to fluorinated and/or chlorinated species, little attention has been directed to the reactions of positive ions with bromine containing molecules. Yet a systematic study of these reactions permits useful comparison with the ion chemistry of fully and partially fluorinated/chlorinated compounds. This in turn improves our fundamental understanding of ion-molecule reactions, and ultimately leads, for example, to better models to predict the optimum conditions needed to operate industrial plasma processes. In this paper the thermal biomolecular rate coefficients and product ion branching ratios for the reactions of the positive ions (in order of increasing recombination energy) H2O+, N2O+, O+, CO2+, CO+, N+, and N2+ with the bromine containing molecules CF3Br, CF2Br2, CFBr3, CF2BrCl, CFBr2Cl, CBrCl3, CH3Br, CH2Br2, CH2FBr, CHF2Br, CHFBr2, CH2BrCl, CHBrCl2, CHBr2Cl, CF3CF2Br, and CF2BrCF2Br at 300 K are reported. This represents the most

  17. The importance of green chemistry in process research and development.

    Science.gov (United States)

    Dunn, Peter J

    2012-02-21

    Green Chemistry or Sustainable Chemistry is defined by the Environmental Protection Agency as "the design of chemical products that reduce or eliminate the use of hazardous substances" In recent years there is a greater societal expectation that chemists and chemical engineers should produce greener and more sustainable chemical processes and it is likely that this trend will continue to grow over the next few decades. This tutorial review gives information on solvents and solvent selection, basic environmental metrics collection and three industrial case histories. All three case histories involve enzymatic chemistry. Pregabalin (Lyrica®) is produced using a lipase based resolution and is extremely unusual in that all four manufacturing steps to make pregabalin are performed in water. Sitagliptin (Januvia®) uses a transaminase in the final chemical step. Finally a rosuvastatin (Crestor®) intermediate is produced using a deoxy ribose aldolase (DERA) enzyme in which two carbon-carbon bonds and two chiral centres are formed in the same process step. PMID:21562677

  18. The importance of green chemistry in process research and development.

    Science.gov (United States)

    Dunn, Peter J

    2012-02-21

    Green Chemistry or Sustainable Chemistry is defined by the Environmental Protection Agency as "the design of chemical products that reduce or eliminate the use of hazardous substances" In recent years there is a greater societal expectation that chemists and chemical engineers should produce greener and more sustainable chemical processes and it is likely that this trend will continue to grow over the next few decades. This tutorial review gives information on solvents and solvent selection, basic environmental metrics collection and three industrial case histories. All three case histories involve enzymatic chemistry. Pregabalin (Lyrica®) is produced using a lipase based resolution and is extremely unusual in that all four manufacturing steps to make pregabalin are performed in water. Sitagliptin (Januvia®) uses a transaminase in the final chemical step. Finally a rosuvastatin (Crestor®) intermediate is produced using a deoxy ribose aldolase (DERA) enzyme in which two carbon-carbon bonds and two chiral centres are formed in the same process step.

  19. An Alternative Approach to the Teaching of Systematic Transition Metal Chemistry.

    Science.gov (United States)

    Hathaway, Brian

    1979-01-01

    Presents an alternative approach to teaching Systematic Transition Metal Chemistry with the transition metal chemistry skeleton features of interest. The "skeleton" is intended as a guide to predicting the chemistry of a selected compound. (Author/SA)

  20. Organic chemistry: Precision pruning of molecules

    Science.gov (United States)

    Yang, Kin S.; Engle, Keary M.

    2016-05-01

    If organic molecules were trees, then the numerous carbon-hydrogen bonds within them would be leaves. A catalyst that targets one 'leaf' out of many similar other ones looks set to be a huge leap for synthetic chemistry. See Letter p.230

  1. Chemistry in one dimension.

    Science.gov (United States)

    Loos, Pierre-François; Ball, Caleb J; Gill, Peter M W

    2015-02-01

    We report benchmark results for one-dimensional (1D) atomic and molecular systems interacting via the Coulomb operator |x|(-1). Using various wavefunction-type approaches, such as Hartree-Fock theory, second- and third-order Møller-Plesset perturbation theory and explicitly correlated calculations, we study the ground state of atoms with up to ten electrons as well as small diatomic and triatomic molecules containing up to two electrons. A detailed analysis of the 1D helium-like ions is given and the expression of the high-density correlation energy is reported. We report the total energies, ionization energies, electron affinities and other physical properties of the many-electron 1D atoms and, using these results, we construct the 1D analog of Mendeleev's periodic table. We find that the 1D periodic table contains only two groups: the alkali metals and the noble gases. We also calculate the dissociation curves of several 1D diatomics and study the chemical bond in H2(+), HeH(2+), He2(3+), H2, HeH(+) and He2(2+). We find that, unlike their 3D counterparts, 1D molecules are primarily bound by one-electron bonds. Finally, we study the chemistry of H3(+) and we discuss the stability of the 1D polymer resulting from an infinite chain of hydrogen atoms. PMID:25518906

  2. Cations form sequence selective motifs within DNA grooves via a combination of cation-pi and ion-dipole/hydrogen bond interactions.

    Directory of Open Access Journals (Sweden)

    Mikaela Stewart

    Full Text Available The fine conformational subtleties of DNA structure modulate many fundamental cellular processes including gene activation/repression, cellular division, and DNA repair. Most of these cellular processes rely on the conformational heterogeneity of specific DNA sequences. Factors including those structural characteristics inherent in the particular base sequence as well as those induced through interaction with solvent components combine to produce fine DNA structural variation including helical flexibility and conformation. Cation-pi interactions between solvent cations or their first hydration shell waters and the faces of DNA bases form sequence selectively and contribute to DNA structural heterogeneity. In this paper, we detect and characterize the binding patterns found in cation-pi interactions between solvent cations and DNA bases in a set of high resolution x-ray crystal structures. Specifically, we found that monovalent cations (Tl⁺ and the polarized first hydration shell waters of divalent cations (Mg²⁺, Ca²⁺ form cation-pi interactions with DNA bases stabilizing unstacked conformations. When these cation-pi interactions are combined with electrostatic interactions a pattern of specific binding motifs is formed within the grooves.

  3. Characterization of the hydrology, water chemistry, and aquatic communities of selected springs in the St. Johns River Water Management District, Florida, 2004

    Science.gov (United States)

    Phelps, G.G.; Walsh, Stephen J.; Gerwig, Robert M.; Tate, William B.

    2006-01-01

    The hydrology, water chemistry, and aquatic communities of Silver Springs, De Leon Spring, Gemini Springs, and Green Spring in the St. Johns River Water Management District, Florida, were studied in 2004 to provide a better understanding of each spring and to compile data of potential use in future water-management decisions. Ground water that discharges from these and other north-central Florida springs originates from the Upper Floridan aquifer of the Floridan aquifer system, a karstic limestone aquifer that extends throughout most of the State's peninsula. This report summarizes data about flow, water chemistry, and aquatic communities, including benthic invertebrates, fishes, algae, and aquatic macrophytes collected by the U.S. Geological Survey, the St. Johns River Water Management District, and the Florida Department of Environmental Protection during 2004, as well as some previously collected data. Differences in water chemistry among these springs reflect local differences in water chemistry in the Upper Floridan aquifer. The three major springs sampled at the Silver Springs group (the Main Spring, Blue Grotto, and the Abyss) have similar proportions of cations and anions but vary in nitrate and dissolved oxygen concentrations. Water from Gemini Springs and Green Spring has higher proportions of sodium and chloride than the Silver Springs group. Water from De Leon Spring also has higher proportions of sodium and chloride than the Silver Springs group but lower proportions of calcium and bicarbonate. Nitrate concentrations have increased over the period of record at all of the springs except Green Spring. Compounds commonly found in wastewater were found in all the springs sampled. The most commonly detected compound was the insect repellant N,N'-diethyl-methyl-toluamide (DEET), which was found in all the springs sampled except De Leon Spring. The pesticide atrazine and its degradate 2-chloro-4-isopropylamino-6-amino-s-triazine (CIAT) were detected in water

  4. Surface chemistry

    CERN Document Server

    Desai, KR

    2008-01-01

    The surface Chemistry of a material as a whole is crucially dependent upon the Nature and type of surfaces exposed on crystallites. It is therefore vitally important to independently Study different, well - defined surfaces through surface analytical techniques. In addition to composition and structure of surface, the subject also provides information on dynamic light scattering, micro emulsions, colloid Stability control and nanostructures. The present book endeavour to bring before the reader that the understanding and exploitation of Solid state phenomena depended largely on the ability to

  5. 选区激光熔化钴铬合金金-瓷结合强度初探%Metal-ceramic bond strength of Co-Cr alloy processed by selective laser melting

    Institute of Scientific and Technical Information of China (English)

    刘洁; 刘洋; 孙荣; 战德松; 王彦岩

    2013-01-01

    Objective To eveluate the metal-ceramic bond strength of a selective laser melting Co-Cr alloy.Methods Twelve Co-Cr metal bars were prepared according to the ISO 9693 standard with Vita porcelain fused onto the centre of each bar.Then the sample bars were devided into two groups of six each.The control group was made by traditional cast process(cast group),and the experimental group was processed by selective laser melting (SLM) technology (SLM group).Metal-ceramic bonding strength and fracture mode were assessed using three-point bending test.Fracture mode analysis was determined by scanning electronic microscope/energy dispersive spectroscopy.Student's t-test was used to analyze the data in SPSS 13.0.Results The metal-ceramic bond strength value of the cast group was (33.45 ±2.34) MPa,and that of the SLM group was (31.62 ± 2.34) MPa (t =0.79,P > 0.05).A mixed fracture mode on the debonding interface of all specimens was observed,while little porcelain was reserved.Conclusions The metal-ceramic system processed by SLM exhibited a bonding strength that satisfies the requirement of clinical application.%目的 采用三点弯曲法评价选区激光熔化钴铬合金金-瓷结合强度,以期为修复临床提供参考.方法 依据ISO 9693标准,分别用铸造法(铸造组)和选区激光熔化法(选区激光熔化组)制作钴铬合金试件,每组6个,试件中间区域熔附瓷粉.三点弯曲法测试金-瓷结合强度,采用SPSS 13.0软件进行t检验,分析两组金-瓷结合强度差异;扫描电镜和能谱仪进行金-瓷结合界面分析.结果 铸造组和选区激光熔化组金-瓷结合强度分别为(33.45 ±2.34)和(31.62 ±2.34) MPa,两组差异无统计学意义(t =0.79,P>0.05).两组试件断裂类型均为混合断裂,仅微量瓷残余.结论 选区激光熔化钴铬合金修复体可满足临床对金-瓷结合强度的要求.

  6. Hydrogen bonded supramolecular structures

    CERN Document Server

    Li, Zhanting

    2015-01-01

    This book covers the advances in the studies of hydrogen-bonding-driven supramolecular systems  made over the past decade. It is divided into four parts, with the first introducing the basics of hydrogen bonding and important hydrogen bonding patterns in solution as well as in the solid state. The second part covers molecular recognition and supramolecular structures driven by hydrogen bonding. The third part introduces the formation of hollow and giant macrocycles directed by hydrogen bonding, while the last part summarizes hydrogen bonded supramolecular polymers. This book is designed to b

  7. 2012 ORGANOMETALLIC CHEMISTRY GRC/GRS, JULY 7-13, 2012

    Energy Technology Data Exchange (ETDEWEB)

    Hillhouse, Gregory

    2012-07-13

    The 2012 Organometallic Chemistry Gordon Research Conference will highlight new basic science and fundamental applications of organometallic chemistry in industrial, academic, and national lab settings. Scientific themes of the conference will include chemical synthesis, reactivity, catalysis, polymer chemistry, bonding, and theory that involve transition-metal (and main-group) interactions with organic moieties.

  8. Surface Morphology and Coordination Chemistry of 4-Isopropylcalix[4]Arene as an Ionophore with Chromium (III) in Fabrication of Cr3+ Selective Membrane Sensor

    International Nuclear Information System (INIS)

    The present work deals with a poly (vinyl chloride) based selective membrane incorporating 4-Isopropylcalix[4]arene as an ionophore which has been prepared and explored as Cr3+ cation selective sensor. The strengths of the ion-ionophore (Cr3+ - 4- Isopropylcalix[4]arene) interactions and the role of ionophore on membrane performance has been studied. The ligand coordination with the ion investigated via IR and UV-Vis spectroscopy. (author)

  9. C-H fluorination: U can fluorinate unactivated bonds

    Science.gov (United States)

    Neumann, Constanze N.; Ritter, Tobias

    2016-09-01

    Introducing C-F bonds into organic molecules is a challenging task, particularly through C-H activation methods. Now, a uranium-based photocatalyst turns traditional selectivity rules on their heads and fluorinates unfunctionalized alkane Csp3-H bonds, even in the presence of C-H bonds that are typically more reactive.

  10. Australia's Bond Home Bias

    OpenAIRE

    Mishra, Anil V; 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 ...

  11. Comparing Carbonyl Chemistry in Comprehensive Introductory Organic Chemistry Textbooks

    Science.gov (United States)

    Nelson, Donna J.; Kumar, Ravi; Ramasamy, Saravanan

    2015-01-01

    Learning the chemistry of compounds containing carbonyl groups is difficult for undergraduate students partly because of a convolution of multiple possible reaction sites, competitive reactions taking place at those sites, different criteria needed to discern between the mechanisms of these reactions, and no straightforward selection method…

  12. Single Molecule Junctions: Probing Contact Chemistry and Fundamental Circuit Laws

    Energy Technology Data Exchange (ETDEWEB)

    Hybertsen M. S.

    2013-04-11

    By exploiting selective link chemistry, formation of single molecule junctions with reproducible conductance has become established. Systematic studies reveal the structure-conductance relationships for diverse molecules. I will draw on experiments from my collaborators at Columbia University, atomic-scale calculations and theory to describe progress in two areas. First, I will describe a novel route to form single molecule junctions, based on SnMe3 terminated molecules, in which gold directly bonds to carbon in the molecule backbone resulting in near ideal contact resistance [1]. Second, comparison of the conductance of junctions formed with molecular species containing either one backbone or two backbones in parallel allows demonstration of the role of quantum interference in the conductance superposition law at the molecular scale [2].

  13. Bond percolation in films

    Science.gov (United States)

    Korneta, W.; Pytel, Z.

    1988-04-01

    Bond percolation in films with simple cubic structure is considered. It is assumed that the probability of a bond being present between nearest-neighbor sites depends on the distances to surfaces. Based on the relation between the Potts model and the bond percolation model, and using the mean-field approximation, the phase diagram and profiles of the percolation probability have been obtained.

  14. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    to think in alternative ways such as issuing corporate bonds. A market for corporate bonds exists in countries such as Norway, Germany, France, the United Kingdom and the United States, while Denmark is still behind in this trend. Some large Danish corporations have instead used foreign corporate bonds...

  15. Environmental control technology survey of selected US strip mining sites. Volume 2B. Alabama. Water quality impacts and overburden chemistry of Alabama study site

    Energy Technology Data Exchange (ETDEWEB)

    Henricks, J D; Bogner, J E; Olsen, R D; Schubert, J P; Sobek, A A; Johnson, D O

    1980-05-01

    As part of a program to examine the ability of existing control technologies to meet federal guidelines for the quality of aqueous effluents from coal mines, an intensive study of water, coal, and overburden chemistry was conducted at a surface coal mine in Alabama from May 1976 through July 1977. Sampling sites included the pit sump, a stream downgrade from the mine, the discharge from the water treatment facility, and a small stream outside the mine drainage. Water samples were collected every two weeks by Argonne subcontractors at the Alabama Geological Survey and analysed for the following parameters: specific conductance, pH, temperature, acidity, bicarbonate, carbonate, chloride, total dissolved solids, suspended solids, sulfate, and 20 metals. Analysis of the coal and overburden shows that no potential acid problem exists at this mine. Water quality is good in both streams sampled, and high levels of dissolved elements are found only in water collected from the pit sump. The mine effluent is in compliance with Office of Surface Mining water quality standards.

  16. 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

  17. Combustion chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Brown, N.J. [Lawrence Berkeley Laboratory, CA (United States)

    1993-12-01

    This research is concerned with the development and use of sensitivity analysis tools to probe the response of dependent variables to model input variables. Sensitivity analysis is important at all levels of combustion modeling. This group`s research continues to be focused on elucidating the interrelationship between features in the underlying potential energy surface (obtained from ab initio quantum chemistry calculations) and their responses in the quantum dynamics, e.g., reactive transition probabilities, cross sections, and thermal rate coefficients. The goals of this research are: (i) to provide feedback information to quantum chemists in their potential surface refinement efforts, and (ii) to gain a better understanding of how various regions in the potential influence the dynamics. These investigations are carried out with the methodology of quantum functional sensitivity analysis (QFSA).

  18. Interface nanochemistry effects on stainless steel diffusion bonding

    Science.gov (United States)

    Cox, M. J.; Carpenter, R. W.; Kim, M. J.

    2002-02-01

    The diffusion-bonding behavior of single-phase austenitic stainless steel depends strongly on the chemistry of the surfaces to be bounded. We found that very smooth (0.5 nm root-mean-square (RMS) roughness), mechanically polished and lapped substrates would bond completely in ultrahigh vacuum (UHV) in 1 hour at 1000 °C under 3.5 MPa uniaxial pressure, if the native oxide on the substrates was removed by ion-beam cleaning, as shown by in-situ Auger analysis. No voids were observed in these bonded interfaces by transmission electron microscopy (TEM), and the strength was equal to that of the unbounded bare material. No bond formed between the substrates if in-situ ion cleaning was not used. The rougher cleaned substrates partially bonded, indicating that roughness, as well as native oxides, reduced the bonding kinetics.

  19. Solvent extraction: the coordination chemistry behind extractive metallurgy.

    Science.gov (United States)

    Wilson, A Matthew; Bailey, Phillip J; Tasker, Peter A; Turkington, Jennifer R; Grant, Richard A; Love, Jason B

    2014-01-01

    The modes of action of the commercial solvent extractants used in extractive hydrometallurgy are classified according to whether the recovery process involves the transport of metal cations, M(n+), metalate anions, MXx(n-), or metal salts, MXx into a water-immiscible solvent. Well-established principles of coordination chemistry provide an explanation for the remarkable strengths and selectivities shown by most of these extractants. Reagents which achieve high selectivity when transporting metal cations or metal salts into a water-immiscible solvent usually operate in the inner coordination sphere of the metal and provide donor atom types or dispositions which favour the formation of particularly stable neutral complexes that have high solubility in the hydrocarbons commonly used in recovery processes. In the extraction of metalates, the structures of the neutral assemblies formed in the water-immiscible phase are usually not well defined and the cationic reagents can be assumed to operate in the outer coordination spheres. The formation of secondary bonds in the outer sphere using, for example, electrostatic or H-bonding interactions are favoured by the low polarity of the water-immiscible solvents.

  20. Photoredox Catalysis in Organic Chemistry

    Science.gov (United States)

    2016-01-01

    In recent years, photoredox catalysis has come to the forefront in organic chemistry as a powerful strategy for the activation of small molecules. In a general sense, these approaches rely on the ability of metal complexes and organic dyes to convert visible light into chemical energy by engaging in single-electron transfer with organic substrates, thereby generating reactive intermediates. In this Perspective, we highlight the unique ability of photoredox catalysis to expedite the development of completely new reaction mechanisms, with particular emphasis placed on multicatalytic strategies that enable the construction of challenging carbon–carbon and carbon–heteroatom bonds. PMID:27477076

  1. Photoredox Catalysis in Organic Chemistry.

    Science.gov (United States)

    Shaw, Megan H; Twilton, Jack; MacMillan, David W C

    2016-08-19

    In recent years, photoredox catalysis has come to the forefront in organic chemistry as a powerful strategy for the activation of small molecules. In a general sense, these approaches rely on the ability of metal complexes and organic dyes to convert visible light into chemical energy by engaging in single-electron transfer with organic substrates, thereby generating reactive intermediates. In this Perspective, we highlight the unique ability of photoredox catalysis to expedite the development of completely new reaction mechanisms, with particular emphasis placed on multicatalytic strategies that enable the construction of challenging carbon-carbon and carbon-heteroatom bonds. PMID:27477076

  2. Photoredox Catalysis in Organic Chemistry.

    Science.gov (United States)

    Shaw, Megan H; Twilton, Jack; MacMillan, David W C

    2016-08-19

    In recent years, photoredox catalysis has come to the forefront in organic chemistry as a powerful strategy for the activation of small molecules. In a general sense, these approaches rely on the ability of metal complexes and organic dyes to convert visible light into chemical energy by engaging in single-electron transfer with organic substrates, thereby generating reactive intermediates. In this Perspective, we highlight the unique ability of photoredox catalysis to expedite the development of completely new reaction mechanisms, with particular emphasis placed on multicatalytic strategies that enable the construction of challenging carbon-carbon and carbon-heteroatom bonds.

  3. Reticular chemistry for clean energy

    Science.gov (United States)

    Yaghi, Omar

    2009-03-01

    Linking molecular building blocks by strong bonds to make networks (Reticular Chemistry) has yielded a number of new classes of materials such as metal-organic frameworks, zeolitic imidazolate frameworks and covalent organic frameworks. These are new classes of porous materials in which inorganic 'joints' are linked by organic 'struts' to give extended structures with surface areas greater than 5000 m2/g. Their ultra-high surface area is useful in storing hydrogen and natural gas, and for capturing carbon dioxide. Recently we have shown that MOFs can be quite effective as air purification and capture of harmful gases. This presentation will highlight the milestones and future prospects of this new field

  4. Bonding thermoplastic polymers

    Science.gov (United States)

    Wallow, Thomas I.; Hunter, Marion C.; Krafcik, Karen Lee; Morales, Alfredo M.; Simmons, Blake A.; Domeier, Linda A.

    2008-06-24

    We demonstrate a new method for joining patterned thermoplastic parts into layered structures. The method takes advantage of case-II permeant diffusion to generate dimensionally controlled, activated bonding layers at the surfaces being joined. It is capable of producing bonds characterized by cohesive failure while preserving the fidelity of patterned features in the bonding surfaces. This approach is uniquely suited to production of microfluidic multilayer structures, as it allows the bond-forming interface between plastic parts to be precisely manipulated at micrometer length scales. The bond enhancing procedure is easily integrated in standard process flows and requires no specialized equipment.

  5. Science Update: Inorganic Chemistry.

    Science.gov (United States)

    Rawls, Rebecca

    1981-01-01

    Describes areas of inorganic chemistry which have changed dramatically in the past year or two, including photochemistry, electrochemistry, organometallic complexes, inorganic reaction theory, and solid state chemistry. (DS)

  6. Environmental control technology survey of selected US strip mining sites. Volume 2A: Ohio: water quality impacts and overburden chemistry of Ohio study site

    Energy Technology Data Exchange (ETDEWEB)

    Bogner, J E; Henricks, J D; Olsen, R D; Schubert, J P; Sobek, A A; Wilkey, M L; Johnson, D O

    1979-05-01

    An intensive study of water, overburden, and coal chemistry was conducted at a large surface mine in Ohio from May 1976 through July 1977. Sampling sites were chosen to include the final mine effluent at the outflow of a large settling pond and chemically-treated drainage from a coal storage pile. Samples were collected semimonthly and analyzed for total dissolved solids, total suspended solids, alkalinity, acidity, sulfate, chloride, and 16 metals. Field measurements included pH, flow rate, dissolved oxygen, and specific conductance. The final effluent, where sampled, generally complied with Office of Surface Mining reclamation standards for pH, iron, and total suspended solids. Comparison of the final effluent with water quality of an unnamed tributary above the mine suggested that elevated values for specific conductance, total dissolved solids, sulfate, calcium, magnesium, manganese, and zinc were attributable to the mine operation. In general, there were observable seasonal variations in flow rates that correlated positively to suspended solids concentrations and negatively to concentrations of dissolved constituents in the final effluent. Drainage from the coal storage pile contained elevated levels of acidity and dissolved metals which were not reduced significantly by the soda ash treatment. The storage pile drainage was diluted, however, by large volumes of alkaline water in the settling pond. Analysis of overburden and coal indicated that the major impact of mine drainage was pyrite oxidation and hydrolysis in the Middle Kittanning Coal and in the Lower Freeport Shale overlying the coal. However, the presence of a calcite-cemented section in the Upper Freeport Sandstone contributed substantial self-neutralizing capacity to the overburden section, resulting in generally alkaline drainage at this site.

  7. Exploring the Nature of the H[subscript 2] Bond. 1. Using Spreadsheet Calculations to Examine the Valence Bond and Molecular Orbital Methods

    Science.gov (United States)

    Halpern, Arthur M.; Glendening, Eric D.

    2013-01-01

    A three-part project for students in physical chemistry, computational chemistry, or independent study is described in which they explore applications of valence bond (VB) and molecular orbital-configuration interaction (MO-CI) treatments of H[subscript 2]. Using a scientific spreadsheet, students construct potential-energy (PE) curves for several…

  8. COMPARATIVE EVALUATION OF THE BONDING EFFICACY OF SIXTH, SEVENTH AND EIGHTH GENERATION BONDING AGENTS: AN IN VITRO STUDY

    OpenAIRE

    Paul Joseph; Chakravarthy Yadav; Kumar Satheesh; Raju Rahna

    2013-01-01

    The aim of the study was to compare In-vitro the micro tensile bond strength of sixth generation (Clearfil SE Bond, Kuraray, Japan), seventh generation (Adper Easy One, 3 M ESPE, Germany) and eighth generation ((Futurabond DC, Voco, Germany) dentin bonding agents. Twenty freshly extracted caries free, unrestored human molars were selected. The occlusal surfaces were ground flat; divided into four groups of five each according to the bonding agent applied and covered with composite resin (10 m...

  9. Assessment of water chemistry, habitat, and benthic macroinvertebrates at selected stream-quality monitoring sites in Chester County, Pennsylvania, 1998-2000

    Science.gov (United States)

    Reif, Andrew G.

    2004-01-01

    Biological, chemical, and habitat data have been collected from a network of sites in Chester County, Pa., from 1970 to 2003 to assess stream quality. Forty sites in 6 major stream basins were sampled between 1998 and 2000. Biological data were used to determine levels of impairment in the benthic-macroinvertebrate community in Chester County streams and relate the impairment, in conjunction with chemical and habitat data, to overall stream quality. Biological data consisted of benthic-macroinvertebrate samples that were collected annually in the fall. Water-chemistry samples were collected and instream habitat was assessed in support of the biological sampling. Most sites in the network were designated as nonimpacted or slightly impacted by human activities or extreme climatic conditions on the basis of biological-metric analysis of benthic-macroinvertebrate data. Impacted sites were affected by factors, such as nutrient enrichment, erosion and sedimentation, point discharges, and droughts and floods. Streams in the Schuylkill River, Delaware River, and East Branch Brandywine Creek Basins in Chester County generally had low nutrient concentrations, except in areas affected by wastewater- treatment discharges, and stream habitat that was affected by erosion. Streams in the West Branch Brandywine, Christina, Big Elk, and Octoraro Creek Basins in Chester County generally had elevated nutrient concentrations and streambottom habitat that was affected by sediment deposition. Macroinvertebrate communities identified in samples from French Creek, Pigeon Creek (Schuylkill River Basin), and East Branch Brandywine Creek at Glenmoore consistently indicate good stream conditions and were the best conditions measured in the network. Macroinvertebrate communities identified in samples from Trout Creek (site 61), West Branch Red Clay Creek (site 55) (Christina River Basin), and Valley Creek near Atglen (site 34) (Octoraro Creek Basin) indicated fair to poor stream conditions and

  10. Trace Chemistry

    Science.gov (United States)

    Radhakrishnan, Krishnan; Whitefield, Philip

    1999-01-01

    The goals of the trace chemistry group were to identify the processes relevant to aerosol and aerosol precursor formation occurring within aircraft gas turbine engines; that is, within the combustor, turbine, and nozzle. The topics of discussion focused on whether the chemistry of aerosol formation is homogeneous or heterogeneous; what species are important for aerosol and aerosol precursor formation; what modeling/theoretical activities to pursue; what experiments to carry out that both support modeling activities and elucidate fundamental processes; and the role of particulates in aerosol and aerosol precursor formation. The consensus of the group was that attention should be focused on SO2, SO3, and aerosols. Of immediate concern is the measurement of the concentration of the species SO3, SO2, H2SO4 OH, HO2, H2O2, O, NO, NO2, HONO, HNO3, CO, and CO2 and particulates in various engines, both those currently in use and those in development. The recommendation was that concentration measurements should be made at both the combustor exit and the engine exit. At each location the above species were classified into one of four categories of decreasing importance, Priority I through IV, as follows: Combustor exit: Priority I species - SO3:SO2 ratio, SO3, SO2, and particulates; Priority II species: OH and O; Priority III species - NO and NO2; and Priority IV species - CO and CO2. For the Engine exit: Priority I species - SO3:SO2 ratio, SO3, SO2,H2SO4, and particulates; Priority II species: OH,HO2, H2O2, and O; Priority III species - NO, NO2, HONO, and HNO3; and Priority IV species - CO and CO2. Table I summarizes the anticipated concentration range of each of these species. For particulate matter, the quantities of interest are the number density, size distribution, and composition. In order to provide data for validating multidimensional reacting flow models, it would be desirable to make 2-D, time-resolved measurements of the concentrations of the above species and

  11. Part 6: The Literature of Inorganic Chemistry, Revised.

    Science.gov (United States)

    Douville, Judith A.

    2002-01-01

    Presents a list of resources on inorganic chemistry that includes general surveys, nomenclature, dictionaries, handbooks, compilations, and treatises. Selected for use by academic and student chemists. (DDR)

  12. Weak bond screening system

    Science.gov (United States)

    Chuang, S. Y.; Chang, F. H.; Bell, J. R.

    Consideration is given to the development of a weak bond screening system which is based on the utilization of a high power ultrasonic (HPU) technique. The instrumentation of the prototype bond strength screening system is described, and the adhesively bonded specimens used in the system developmental effort are detailed. Test results obtained from these specimens are presented in terms of bond strength and level of high power ultrasound irradiation. The following observations were made: (1) for Al/Al specimens, 2.6 sec of HPU irradiation will screen weak bond conditions due to improper preparation of bonding surfaces; (2) for composite/composite specimens, 2.0 sec of HPU irradiation will disrupt weak bonds due to under-cured conditions; (3) for Al honeycomb core with composite skin structure, 3.5 sec of HPU irradiation will disrupt weak bonds due to bad adhesive or oils contamination of bonding surfaces; and (4) for Nomex honeycomb with Al skin structure, 1.3 sec of HPU irradiation will disrupt weak bonds due to bad adhesive.

  13. Molten fluoride fuel salt chemistry

    International Nuclear Information System (INIS)

    The chemistry of molten fluorides is traced from their development as fuels in the Molten Salt Reactor Experiment with important factors in their selection being discussed. Key chemical characteristics such as solubility, redox behavior, and chemical activity are explained as they relate to the behavior of molten fluoride fuel systems. Fission product behavior is described along with processing experience. Development requirements for fitting the current state of the chemistry to modern nuclear fuel system are described. It is concluded that while much is known about molten fluoride behavior, processing and recycle of the fuel components is a necessary factor if future systems are to be established

  14. 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

    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...

  15. Green chemistry oriented organic synthesis in water.

    Science.gov (United States)

    Simon, Marc-Olivier; Li, Chao-Jun

    2012-02-21

    The use of water as solvent features many benefits such as improving reactivities and selectivities, simplifying the workup procedures, enabling the recycling of the catalyst and allowing mild reaction conditions and protecting-group free synthesis in addition to being benign itself. In addition, exploring organic chemistry in water can lead to uncommon reactivities and selectivities complementing the organic chemists' synthetic toolbox in organic solvents. Studying chemistry in water also allows insight to be gained into Nature's way of chemical synthesis. However, using water as solvent is not always green. This tutorial review briefly discusses organic synthesis in water with a Green Chemistry perspective. PMID:22048162

  16. Green chemistry oriented organic synthesis in water.

    Science.gov (United States)

    Simon, Marc-Olivier; Li, Chao-Jun

    2012-02-21

    The use of water as solvent features many benefits such as improving reactivities and selectivities, simplifying the workup procedures, enabling the recycling of the catalyst and allowing mild reaction conditions and protecting-group free synthesis in addition to being benign itself. In addition, exploring organic chemistry in water can lead to uncommon reactivities and selectivities complementing the organic chemists' synthetic toolbox in organic solvents. Studying chemistry in water also allows insight to be gained into Nature's way of chemical synthesis. However, using water as solvent is not always green. This tutorial review briefly discusses organic synthesis in water with a Green Chemistry perspective.

  17. Response of Stream Chemistry During Base Flow to Gradients of Urbanization in Selected Locations Across the Conterminous United States, 2002-04

    Science.gov (United States)

    Sprague, Lori A.; Harned, Douglas A.; Hall, David W.; Nowell, Lisa H.; Bauch, Nancy J.; Richards, Kevin D.

    2007-01-01

    During 2002-2004, the U.S. Geological Survey's National Water-Quality Assessment Program conducted a study to determine the effects of urbanization on stream water quality and aquatic communities in six environmentally heterogeneous areas of the conterminous United States--Atlanta, Georgia; Raleigh-Durham, North Carolina; Milwaukee-Green Bay, Wisconsin; Dallas-Fort Worth, Texas; Denver, Colorado; and Portland, Oregon. This report compares and contrasts the response of stream chemistry during base flow to urbanization in different environmental settings and examines the relation between the exceedance of water-quality benchmarks and the level of urbanization in these areas. Chemical characteristics studied included concentrations of nutrients, dissolved pesticides, suspended sediment, sulfate, and chloride in base flow. In three study areas where the background land cover in minimally urbanized basins was predominantly forested (Atlanta, Raleigh-Durham, and Portland), urban development was associated with increased concentrations of nitrogen and total herbicides in streams. In Portland, there was evidence of mixed agricultural and urban influences at sites with 20 to 50 percent urban land cover. In two study areas where agriculture was the predominant background land cover (Milwaukee-Green Bay and Dallas-Fort Worth), concentrations of nitrogen and herbicides were flat or decreasing as urbanization increased. In Denver, which had predominantly shrub/grass as background land cover, nitrogen concentrations were only weakly related to urbanization, and total herbicide concentrations did not show any clear pattern relative to land cover - perhaps because of extensive water management in the study area. In contrast, total insecticide concentrations increased with increasing urbanization in all six study areas, likely due to high use of insecticides in urban applications and, for some study areas, the proximity of urban land cover to the sampling sites. Phosphorus

  18. Structure, chemistry, and properties of mineral nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Waychunas, G.A.; Zhang, H.; Gilbert, B.

    2008-12-02

    Nanoparticle properties can depart markedly from their bulk analog materials, including large differences in chemical reactivity, molecular and electronic structure, and mechanical behavior. The greatest changes are expected at the smallest sizes, e.g. 10 nm and below, where surface effects are expected to dominate bonding, shape and energy considerations. The precise chemistry at nanoparticle interfaces can have a profound effect on structure, phase transformations, strain, and reactivity. Certain phases may exist only as nanoparticles, requiring transformations in chemistry, stoichiometry and structure with evolution to larger sizes. In general, mineralogical nanoparticles have been little studied.

  19. Ab initio valence calculations in chemistry

    CERN Document Server

    Cook, D B

    1974-01-01

    Ab Initio Valence Calculations in Chemistry describes the theory and practice of ab initio valence calculations in chemistry and applies the ideas to a specific example, linear BeH2. Topics covered include the Schrödinger equation and the orbital approximation to atomic orbitals; molecular orbital and valence bond methods; practical molecular wave functions; and molecular integrals. Open shell systems, molecular symmetry, and localized descriptions of electronic structure are also discussed. This book is comprised of 13 chapters and begins by introducing the reader to the use of the Schrödinge

  20. Halogen Bonding or Hydrogen Bonding between 2,2,6,6-Tetramethyl-piperidine-noxyl Radical and Trihalomethanes CHX3 (X=Cl, Br, I)

    Institute of Scientific and Technical Information of China (English)

    Xiao-ran Zhao; Xue Pang; Xiao-qing Yan; Wei-jun Jin

    2013-01-01

    The halogen and hydrogen bonding complexes between 2,2,6,6-tetramethylpiperidine-noxyl and trihalomethanes (CHX3,X=Cl,Br,I) are simulated by computational quantum chemistry.The molecular electrostatic potentials,geometrical parameters and interaction energy of halogen and hydrogen bonding complexes combined with natural bond orbital analysis are obtained.The results indicate that both halogen and hydrogen bonding interactions obey the order Cl<Br<I,and hydrogen bonding is stronger than the corresponding halogen bond ing.So,hydrogen bonding complexes should be dominant in trihalomethanes.However,it is possible that halogen bonding complex is competitive,even preponderant,in triiodomethane due to the similar interaction energy.This work might provide useful information on specific solvent effects as well as for understanding the mechanism of nitroxide radicals as a bioprobe to interact with the halogenated compounds in biological and biochemical fields.

  1. Selected aspects of the chemistry and radiation chemistry of lignin

    International Nuclear Information System (INIS)

    Lignin was subjected to electron and gamma radiation as part of a study to determine the effects of radiation on its structure. Some of the factors that influence the outcome of the treatment are the dose, the nature of the atmosphere surrounding the sample, and the physical state and nature of the irradiated lignin itself. Our data describe some of the free radical intermediates formed during irradiation and how the variation of certain factors affects the magnitude and direction of the effects induced by irradiation. The data were obtained using electron spin resonance spectroscopy, size exclusion chromatography and other high performance liguid chromatography techniques and gas chromatography-mass spectroscopy analysis. The substrates used were Indulin AT and pyrolysed lignin. Depending on the experimental conditions, radiation treatment may lead to either polymerisation or degradation processes. The factors that determine the outcome are discussed in terms of substrate structures and the chemical processes that take place. (author) 12 refs

  2. Selected topics in high temperature chemistry defect chemistry of solids

    CERN Document Server

    Johannesen, Ø

    2013-01-01

    The properties of materials at high temperature play a vital role in their processing and practical use. The real properties of materials at elevated temperatures are very often governed by defects in their structure. Lattice defects may consist of point defects like vacancies, interstitial atoms or substituted atoms. These classes are discussed in general and specifically for oxides, nitrides, carbides and sulfides. Defect aggregates, shear structures and adaptive structures are also described. Special attention is paid to hydrogen defects which seem to play an important role in several mater

  3. Influence of Selected Alkoxysilanes on Dispersive Properties and Surface Chemistry of Titanium Dioxide and TiO2–SiO2 Composite Material

    Directory of Open Access Journals (Sweden)

    Katarzyna Siwińska-Stefańska

    2012-01-01

    Full Text Available The paper reports on characterisation of titanium dioxide and coprecipitated TiO2–SiO2 composite material functionalised with selected alkoxysilanes. Synthetic composite material was obtained by an emulsion method with cyclohexane as the organic phase, titanium sulfate as titanium precursor, and sodium silicate solution as precipitating agent were applied. Structures of titania and composite material samples were studied by the wide angle X-ray scattering method. The chemical composition of TiO2–SiO2 composite material precipitated was evaluated based on the energy dispersive X-ray spectroscopy technique. The functionalised TiO2 and TiO2–SiO2 composite material were thoroughly characterised to determine the yield of functionalisation with silanes. The characterisation included determination of dispersion and morphology of the systems (particle size distribution, scanning electron microscope images, adsorption properties (nitrogen adsorption isotherms, and electrokinetic properties (zeta potential.

  4. 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...

  5. Equilibrium CO bond lengths

    Science.gov (United States)

    Demaison, Jean; Császár, Attila G.

    2012-09-01

    Based on a sample of 38 molecules, 47 accurate equilibrium CO bond lengths have been collected and analyzed. These ultimate experimental (reEX), semiexperimental (reSE), and Born-Oppenheimer (reBO) equilibrium structures are compared to reBO estimates from two lower-level techniques of electronic structure theory, MP2(FC)/cc-pVQZ and B3LYP/6-311+G(3df,2pd). A linear relationship is found between the best equilibrium bond lengths and their MP2 or B3LYP estimates. These (and similar) linear relationships permit to estimate the CO bond length with an accuracy of 0.002 Å within the full range of 1.10-1.43 Å, corresponding to single, double, and triple CO bonds, for a large number of molecules. The variation of the CO bond length is qualitatively explained using the Atoms in Molecules method. In particular, a nice correlation is found between the CO bond length and the bond critical point density and it appears that the CO bond is at the same time covalent and ionic. Conditions which permit the computation of an accurate ab initio Born-Oppenheimer equilibrium structure are discussed. In particular, the core-core and core-valence correlation is investigated and it is shown to roughly increase with the bond length.

  6. The Bond Market's q

    OpenAIRE

    Thomas Philippon

    2006-01-01

    I propose an implementation of the q-theory of investment using bond prices instead of equity prices. Credit risk makes corporate bond prices sensitive to future asset values, and q can be inferred from bond prices. The bond market's q performs much better than the usual measure in standard investment equations. With aggregate data, the fit is three times better, cash flows are driven out and the implied adjustment costs are reduced by more than an order of magnitude. The new measure also imp...

  7. Radiation chemistry research using PULAF

    Science.gov (United States)

    Gaikwad, Parimal; Priyadarsini, K. I.; Rao, B. S. M.

    2008-10-01

    The details of the recently installed 7 MeV Pune University LINAC Facility (PULAF) coupled with the optical absorption technique for pulse radiolysis studies at the National Centre for Free Radical Research, Department of Chemistry, University of Pune, Pune, India are described. The facility has a selection of electron pulse widths in the range 10 ns-3 μs with corresponding doses of about 5-144 Gy per pulse. The operation of the machine and the detection system are fully automated. Several researchers from various Indian universities and national laboratories use the PULAF and some of the projects that are currently undertaken by our group and others include the radiation chemistry of indole and chalcone derivatives, herbal antioxidants, structure-reactivity studies in cinnamates, redox chemistry of inorganic metal complexes, studies on oxidation of pyrimidine analogues and aromatic sulphur compounds. Some of them are briefly discussed here.

  8. Radiation chemistry research using PULAF

    Energy Technology Data Exchange (ETDEWEB)

    Gaikwad, Parimal [National Centre for Free Radical Research, Department of Chemistry, University of Pune, Pune 411 007 (India); Priyadarsini, K.I. [Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085 (India); Rao, B.S.M. [National Centre for Free Radical Research, Department of Chemistry, University of Pune, Pune 411 007 (India)], E-mail: bsmr@chem.unipune.ernet.in

    2008-10-15

    The details of the recently installed 7 MeV Pune University LINAC Facility (PULAF) coupled with the optical absorption technique for pulse radiolysis studies at the National Centre for Free Radical Research, Department of Chemistry, University of Pune, Pune, India are described. The facility has a selection of electron pulse widths in the range 10 ns-3 {mu}s with corresponding doses of about 5-144 Gy per pulse. The operation of the machine and the detection system are fully automated. Several researchers from various Indian universities and national laboratories use the PULAF and some of the projects that are currently undertaken by our group and others include the radiation chemistry of indole and chalcone derivatives, herbal antioxidants, structure-reactivity studies in cinnamates, redox chemistry of inorganic metal complexes, studies on oxidation of pyrimidine analogues and aromatic sulphur compounds. Some of them are briefly discussed here.

  9. Mass spectrometry. [in organic chemistry

    Science.gov (United States)

    Burlingame, A. L.; Shackleton, C. H. L.; Howe, I.; Chizhov, O. S.

    1978-01-01

    A review of mass spectrometry in organic chemistry is given, dealing with advances in instrumentation and computer techniques, selected topics in gas-phase ion chemistry, and applications in such fields as biomedicine, natural-product studies, and environmental pollution analysis. Innovative techniques and instrumentation are discussed, along with chromatographic-mass spectrometric on-line computer techniques, mass spectral interpretation and management techniques, and such topics in gas-phase ion chemistry as electron-impact ionization and decomposition, photoionization, field ionization and desorption, high-pressure mass spectrometry, ion cyclotron resonance, and isomerization reactions of organic ions. Applications of mass spectrometry are examined with respect to bio-oligomers and their constituents, biomedically important substances, microbiology, environmental organic analysis, and organic geochemistry.

  10. Distributed scaffolding: Wiki collaboration among Latino high school chemistry students

    Science.gov (United States)

    O'Sullivan, Edwin Duncan, Jr.

    The primary purpose of this study was to evaluate if wiki collaboration among Latino high school chemistry students can help reduce the science achievement gap between Latino and White students. The study was a quasi-experimental pre/post control group mixed-methods design. It used three intact sections of a high school chemistry course. The first research question asked if there is a difference in academic achievement between a treatment and control group on selected concepts from the topics of bonding, physical changes, and chemical changes, when Latino high school chemistry students collaborate on a quasi-natural wiki project. Overall results for all three activities (Bonding, Physical Changes, and Chemical Changes) indicated no significant difference between the wiki and control group. However, students performing the chemical changes activity did significantly better than their respective control group. Furthermore, there was a significant association, with large effect size, between group membership and ability to overcome the misconception that aqueous ionic reactants in precipitation reactions exist as molecular pairs of ions. Qualitative analysis of classroom and computer lab dialogue, discussion board communication, student focus groups, teacher interviews, and wiki content attributes the better performance of the chemical changes wiki group to favorable differences in intersubjectivity and calibrated assistance, as well as learning about submicroscopic representations of precipitation reactions in multiple contexts. Furthermore, the nonsignificant result overall points to an aversion to peer editing as a possible cause. Drawing considerably on Vygotsky and Piaget, the results are discussed within the context of how distributed scaffolding facilitated medium levels of cognitive conflict. The second research question asked what the characteristics of distributed metacognitive scaffolding are when Latino high school chemistry students collaborate on a quasi

  11. Dentin-bonding agents

    Directory of Open Access Journals (Sweden)

    João Carlos Gomes

    2008-01-01

    Full Text Available New dental restorative materials have been developed to meet not only the functional demands, but esthetics as well, and in the last few years an enormous range of new materials has appeared for use in dentistry. Among them, several adhesive systems, and different operative techniques for each group materials. Therefore, is indispensable for the professional to know about the properties, characteristics, and association of these materials with the dental structures, in order to select and use them correctly. Should conventional self-etching adhesive systems be used? This question encouraged this literature review to be conducted, with the aim of comparing the conventional adhesive systems with the self-etching systems and to look for scientific data that would help professionals to choose which adhesive system to use. When compared to conventional systems, it was noted that the self-etching systems show less sensitivity to technique, especially as regards errors the operator could commit. The self-etching systems, particularly the 2-step type, have shown equivalent values of bond strength, marginal microleakage and performance, therefore, will be an option for direct composite resin restorations in posterior teeth.

  12. Selective Preference of Parallel DNA Triplexes Is Due to the Disruption of Hoogsteen Hydrogen Bonds Caused by the Severe Nonisostericity between the G*GC and T*AT Triplets

    Science.gov (United States)

    Goldsmith, Gunaseelan; Rathinavelan, Thenmalarchelvi; Yathindra, Narayanarao

    2016-01-01

    Implications of DNA, RNA and RNA.DNA hybrid triplexes in diverse biological functions, diseases and therapeutic applications call for a thorough understanding of their structure-function relationships. Despite exhaustive studies mechanistic rationale for the discriminatory preference of parallel DNA triplexes with G*GC & T*AT triplets still remains elusive. Here, we show that the highest nonisostericity between the G*GC & T*AT triplets imposes extensive stereochemical rearrangements contributing to context dependent triplex destabilisation through selective disruption of Hoogsteen scheme of hydrogen bonds. MD simulations of nineteen DNA triplexes with an assortment of sequence milieu reveal for the first time fresh insights into the nature and extent of destabilization from a single (non-overlapping), double (overlapping) and multiple pairs of nonisosteric base triplets (NIBTs). It is found that a solitary pair of NIBTs, feasible either at a G*GC/T*AT or T*AT/G*GC triplex junction, does not impinge significantly on triplex stability. But two overlapping pairs of NIBTs resulting from either a T*AT or a G*GC interruption disrupt Hoogsteen pair to a noncanonical mismatch destabilizing the triplex by ~10 to 14 kcal/mol, implying that their frequent incidence in multiples, especially, in short sequences could even hinder triplex formation. The results provide (i) an unambiguous and generalised mechanistic rationale for the discriminatory trait of parallel triplexes, including those studied experimentally (ii) clarity for the prevalence of antiparallel triplexes and (iii) comprehensive perspectives on the sequence dependent influence of nonisosteric base triplets useful in the rational design of TFO’s against potential triplex target sites. PMID:27010368

  13. Selective Preference of Parallel DNA Triplexes Is Due to the Disruption of Hoogsteen Hydrogen Bonds Caused by the Severe Nonisostericity between the G*GC and T*AT Triplets.

    Science.gov (United States)

    Goldsmith, Gunaseelan; Rathinavelan, Thenmalarchelvi; Yathindra, Narayanarao

    2016-01-01

    Implications of DNA, RNA and RNA.DNA hybrid triplexes in diverse biological functions, diseases and therapeutic applications call for a thorough understanding of their structure-function relationships. Despite exhaustive studies mechanistic rationale for the discriminatory preference of parallel DNA triplexes with G*GC & T*AT triplets still remains elusive. Here, we show that the highest nonisostericity between the G*GC & T*AT triplets imposes extensive stereochemical rearrangements contributing to context dependent triplex destabilisation through selective disruption of Hoogsteen scheme of hydrogen bonds. MD simulations of nineteen DNA triplexes with an assortment of sequence milieu reveal for the first time fresh insights into the nature and extent of destabilization from a single (non-overlapping), double (overlapping) and multiple pairs of nonisosteric base triplets (NIBTs). It is found that a solitary pair of NIBTs, feasible either at a G*GC/T*AT or T*AT/G*GC triplex junction, does not impinge significantly on triplex stability. But two overlapping pairs of NIBTs resulting from either a T*AT or a G*GC interruption disrupt Hoogsteen pair to a noncanonical mismatch destabilizing the triplex by ~10 to 14 kcal/mol, implying that their frequent incidence in multiples, especially, in short sequences could even hinder triplex formation. The results provide (i) an unambiguous and generalised mechanistic rationale for the discriminatory trait of parallel triplexes, including those studied experimentally (ii) clarity for the prevalence of antiparallel triplexes and (iii) comprehensive perspectives on the sequence dependent influence of nonisosteric base triplets useful in the rational design of TFO's against potential triplex target sites. PMID:27010368

  14. Selective Preference of Parallel DNA Triplexes Is Due to the Disruption of Hoogsteen Hydrogen Bonds Caused by the Severe Nonisostericity between the G*GC and T*AT Triplets.

    Directory of Open Access Journals (Sweden)

    Gunaseelan Goldsmith

    Full Text Available Implications of DNA, RNA and RNA.DNA hybrid triplexes in diverse biological functions, diseases and therapeutic applications call for a thorough understanding of their structure-function relationships. Despite exhaustive studies mechanistic rationale for the discriminatory preference of parallel DNA triplexes with G*GC & T*AT triplets still remains elusive. Here, we show that the highest nonisostericity between the G*GC & T*AT triplets imposes extensive stereochemical rearrangements contributing to context dependent triplex destabilisation through selective disruption of Hoogsteen scheme of hydrogen bonds. MD simulations of nineteen DNA triplexes with an assortment of sequence milieu reveal for the first time fresh insights into the nature and extent of destabilization from a single (non-overlapping, double (overlapping and multiple pairs of nonisosteric base triplets (NIBTs. It is found that a solitary pair of NIBTs, feasible either at a G*GC/T*AT or T*AT/G*GC triplex junction, does not impinge significantly on triplex stability. But two overlapping pairs of NIBTs resulting from either a T*AT or a G*GC interruption disrupt Hoogsteen pair to a noncanonical mismatch destabilizing the triplex by ~10 to 14 kcal/mol, implying that their frequent incidence in multiples, especially, in short sequences could even hinder triplex formation. The results provide (i an unambiguous and generalised mechanistic rationale for the discriminatory trait of parallel triplexes, including those studied experimentally (ii clarity for the prevalence of antiparallel triplexes and (iii comprehensive perspectives on the sequence dependent influence of nonisosteric base triplets useful in the rational design of TFO's against potential triplex target sites.

  15. Understanding the molecular-level chemistry of water plasmas and the effects of surface modification and deposition on a selection of oxide substrates

    Science.gov (United States)

    Trevino, Kristina J.

    2011-12-01

    This dissertation first examines electrical discharges used to study wastewater samples for contaminant detection and abatement. Two different water samples contaminated with differing concentrations of either methanol (MeOH) or methyl tert-butyl ether (MTBE) were used to follow breakdown mechanisms. Emission from CO* was used to monitor the contaminant and for molecular breakdown confirmation through actinometric OES as it can only arise from the carbon-based contaminant in either system. Detection was achieved at concentrations as low as 0.01 ppm, and molecular decomposition was seen at a variety of plasma parameters. This dissertation also explores the vibrational (thetaV), rotational (thetaR) and translational (thetaT) temperatures for a range of diatomic species in different plasma systems. For the majority of the plasma species studied, thetaV are much higher than thetaR and thetaT. This suggests that more energy is partitioned into the vibrational degrees of freedom in our plasmas. The thetaR reported are significantly lower in all the plasma systems studied and this is a result of radical equilibration to the plasma gas temperature. thetaT values show two characteristics; (1) they are less than the thetaV and higher than the theta R and (2) show varying trends with plasma parameters. Radical energetics were examined through comparison of thetaR, thetaT, and thetaV, yielding significant insight on the partitioning of internal and kinetic energies in plasmas. Correlations between energy partitioning results and corresponding radical surface scattering coefficients obtained using our imaging of radicals interacting with surfaces (IRIS) technique are also presented. Another aspect of plasma process chemistry, namely surface modification via plasma treatment, was investigated through characterization of metal oxides (SiOxNy, nat-SiO2, and dep-SiO2) following their exposure to a range of plasma discharges. Here, emphasis was placed on the surface wettability

  16. Industrial Chemistry and School Chemistry: Making Chemistry Studies More Relevant

    Science.gov (United States)

    Hofstein, Avi; Kesner, Miri

    2006-01-01

    In this paper, we present the development and implementation over the period of more than 15 years of learning materials focusing on industrial chemistry as the main theme. The work was conducted in the Department of Science Teaching at the Weizmann Institute of Science, Israel. The project's general goal was to teach chemistry concepts in the…

  17. Gender Inclusivity in Secondary Chemistry: A Study of Male and Female Participation in Secondary School Chemistry

    Science.gov (United States)

    Cousins, Andrew

    2007-01-01

    This paper gives a nuanced analysis of participation rates in secondary chemistry by developing the "story" behind national trends and subject selection patterns within an independent school located in a large Australian city. It supplements the documented quantitative data by presenting a case-study where 30 Year 12 chemistry students were…

  18. Organic chemistry on solid surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Zhen; Zaera, Francisco [Department of Chemistry, University of California, Riverside, CA 92521 (United States)

    2006-07-15

    Chemistry on solid surfaces is central to many areas of practical interest such as heterogeneous catalysis, tribology, electrochemistry, and materials processing. With the development of many surface-sensitive analytical techniques in the past decades, great advances have been possible in our understanding of such surface chemistry at the molecular level. Earlier studies with model systems, single crystals in particular, have provided rich information about the adsorption and reaction kinetics of simple inorganic molecules. More recently, the same approach has been expanded to the study of the surface chemistry of relatively complex organic molecules, in large measure in connection with the selective synthesis of fine chemicals and pharmaceuticals. In this report, the chemical reactions of organic molecules and fragments on solid surfaces, mainly on single crystals of metals but also on crystals of metal oxides, carbides, nitrides, phosphides, sulfides and semiconductors as well as on more complex models such as bimetallics, alloys, and supported particles, are reviewed. A scheme borrowed from the organometallic and organic chemistry literature is followed in which key examples of representative reactions are cited first, and general reactivity trends in terms of both the reactants and the nature of the surface are then identified to highlight important mechanistic details. An attempt has been made to emphasize recent advances, but key earlier examples are cited as needed. Finally, correlations between surface and organometallic and organic chemistry, the relevance of surface reactions to applied catalysis and materials functionalization, and some promising future directions in this area are briefly discussed. (author)

  19. Questa baseline and pre-mining ground-water quality investigation. 20. Water chemistry of the Red River and selected seeps, tributaries, and precipitation, Taos County, New Mexico, 2000-2004

    Science.gov (United States)

    Verplanck, P.L.; McCleskey, R.B.; Nordstrom, D.K.

    2006-01-01

    As part of a multi-year project to infer the pre-mining ground-water quality at Molycorp's Questa mine site, surface-water samples of the Red River, some of its tributaries, seeps, and snow samples were collected for analysis of inorganic solutes and of water and sulfate stable isotopes in selected samples. The primary aim of this study was to document diel, storm event, and seasonal variations in water chemistry for the Red River and similar variations in water chemistry for Straight Creek, a natural analog site similar in topography, hydrology, and geology to the mine site for inferring pre-mining water-quality conditions. Red River water samples collected between 2000 and 2004 show that the largest variations in water chemistry occur during late summer rainstorms, often monsoonal in nature. Within hours, discharge of the Red River increased from 8 to 102 cubic feet per second and pH decreased from 7.80 to 4.83. The highest concentrations of metals (iron, aluminum, zinc, manganese) and sulfate also occur during such events. Low-pH and high-solute concentrations during rainstorm runoff are derived primarily from alteration 'scar' areas of naturally high mineralization combined with steep topography that exposes continually altered rock because erosion is too rapid for vegetative growth. The year 2002 was one of the driest on record, and Red River discharge reflected the low seasonal snow pack. No snowmelt peak appeared in the hydrograph record, and a late summer storm produced the highest flow for the year. Snowmelt was closer to normal during 2003 and demonstrated the dilution effect of snowmelt on water chemistry. Two diel sampling events were conducted for the Red River, one during low flow and the other during high flow, at two locations, at the Red River gaging station and just upstream from Molycorp's mill site. No discernible diel trends were observed except for dissolved zinc and manganese at the upstream site during low flow. Straight Creek drainage water

  20. Comparison of Gold Bonding with Mercury Bonding

    NARCIS (Netherlands)

    Kraka, Elfi; Filatov, Michael; Cremer, Dieter

    2009-01-01

    Nine AuX molecules (X = H, O, S, Se, Te, F, Cl, Br, I), their isoelectronic HgX(+) analogues, and the corresponding neutral HgX diatomics have been investigated using NESC (Normalized Elimination of the Small Component) and B3LYP theory to determine relativistic effects for bond dissociation energie

  1. A Química Quântica na compreensão de teorias de Química Orgânica The Quantum Chemistry in the understanding of theories of Organic Chemistry

    Directory of Open Access Journals (Sweden)

    Régis Casimiro Leal

    2010-01-01

    Full Text Available Quantum chemical calculations were performed in order to obtain molecular properties such as electronic density, dipole moment, atomic charges, and bond lengths, which were compared to qualitative results based on the theories of the organic chemistry. The quantum chemistry computational can be a useful tool to support the main theories of the organic chemistry.

  2. From Matter to Life:Chemistry?Chemistry!

    Institute of Scientific and Technical Information of China (English)

    Jean-Marie; LEHN

    2007-01-01

    1 Results Animate as well as inanimate matter,living organisms as well as materials,are formed of molecules and of the organized entities resulting from the interaction of molecules with each other.Chemistry provides the bridge between the molecules of inanimate matter and the highly complex molecular architectures and systems which make up living organisms. Synthetic chemistry has developed a very powerful set of methods for constructing ever more complex molecules.Supramolecular chemistry seeks to con...

  3. Green chemistry: A tool in Pharmaceutical Chemistry

    OpenAIRE

    Smita Talaviya; Falguni Majumdar

    2012-01-01

    Green chemistry expresses an area of research developing from scientific discoveries about pollution awareness and it utilizes a set of principles that reduces or eliminates the use or generation of hazardous substances in all steps of particular synthesis or process. Chemists and medicinal scientists can greatly reduce the risk to human health and the environment by following all the valuable principles of green chemistry. The most simple and direct way to apply green chemistry in pharmaceut...

  4. Nuclear radiation as a probe of chemical bonding: the current interplay between theory and experiment

    Energy Technology Data Exchange (ETDEWEB)

    Newton, M D

    1978-01-01

    After a survey of appropriate theoretical formalisms, recent confrontations of theory and experiment in the areas of neutron scattering, Moessbauer spectroscopy, and positron chemistry are discussed, with major emphasis on the degree to which simple concepts of chemical bonding can be refined by complementary use of the above experimental probes and the powerful techniques of computational quantum chemistry.

  5. Coupled valence bond theory

    NARCIS (Netherlands)

    Havenith, R.W.A.

    2005-01-01

    In this Letter, the formulation and implementation of a parallel response property code for non-orthogonal, valence bond wave-functions are described. Test calculations on benzene and cyclobutadiene show that the polarisability and magnetisability tensors obtained using valence bond theory are compa

  6. Bonded labour in Pakistan

    OpenAIRE

    Ercelawn, Aly; Nauman, Muhammad

    2001-01-01

    Examines the continuing prevalence of debt bondage in the 1990s despite the introduction of national legislation banning the practice. Makes recommendations to the Government and the international community for actions to be taken to eliminate bonded labour and provide rehabilitation for freed workers. Includes texts of Land Reforms Regulations, 1972, the Sindh Tenancy Act, 1950 and the Bonded Labour System (Abolition) Act, 1992.

  7. Hydrogen bonding in polyanilines

    Energy Technology Data Exchange (ETDEWEB)

    Bahceci, S. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey)); Toppare, L. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey)); Yurtsever, E. (Department of Chemistry, Middle East Technical University, Ankara 06531 (Turkey))

    1994-11-29

    Hydrogen bonding between poly(bisphenol A carbonate) (PC) and polyaniline (PAn) is analyzed using semi-empirical quantum methodology. Fully optimized AM1 molecular orbital calculations are reported for various aniline structures (monomer, dimer and trimer), the monomer of the PC and the hydrogen-bonded model of PAn-PC oligomer. ((orig.))

  8. The dissociative bond.

    Science.gov (United States)

    Gordon, Nirit

    2013-01-01

    Dissociation leaves a psychic void and a lingering sense of psychic absence. How do 2 people bond while they are both suffering from dissociation? The author explores the notion of a dissociative bond that occurs in the aftermath of trauma--a bond that holds at its core an understanding and shared detachment from the self. Such a bond is confined to unspoken terms that are established in the relational unconscious. The author proposes understanding the dissociative bond as a transitional space that may not lead to full integration of dissociated knowledge yet offers some healing. This is exemplified by R. Prince's (2009) clinical case study. A relational perspective is adopted, focusing on the intersubjective aspects of a dyadic relationship. In the dissociative bond, recognition of the need to experience mutual dissociation can accommodate a psychic state that yearns for relationship when the psyche cannot fully confront past wounds. Such a bond speaks to the need to reestablish a sense of human relatedness and connection when both parties in the relationship suffer from disconnection. This bond is bound to a silence that becomes both a means of protection against the horror of traumatic memory and a way to convey unspoken gestures toward the other.

  9. The samurai bond market

    OpenAIRE

    Frank Packer; Elizabeth Reynolds

    1997-01-01

    Issuance in the samurai bond market has more than tripled over the past several years. Some observers have attributed this growth to a systematic underestimation of credit risk in the market. A detailed review of credit quality, ratings differences, and initial issue pricing in the samurai bond market, however, turns up little evidence to support this concern.

  10. Chemistry Rocks: Redox Chemistry as a Geologic Tool.

    Science.gov (United States)

    Burns, Mary Sue

    2001-01-01

    Applies chemistry to earth science, uses rocks in chemistry laboratories, and teaches about transition metal chemistry, oxidation states, and oxidation-reduction reactions from firsthand experiences. (YDS)

  11. Wood Bond Testing

    Science.gov (United States)

    1989-01-01

    A joint development program between Hartford Steam Boiler Inspection Technologies and The Weyerhaeuser Company resulted in an internal bond analyzer (IBA), a device which combines ultrasonics with acoustic emission testing techniques. It is actually a spinoff from a spinoff, stemming from a NASA Lewis invented acousto-ultrasonic technique that became a system for testing bond strength of composite materials. Hartford's parent company, Acoustic Emission Technology Corporation (AET) refined and commercialized the technology. The IBA builds on the original system and incorporates on-line process control systems. The IBA determines bond strength by measuring changes in pulsar ultrasonic waves injected into a board. Analysis of the wave determines the average internal bond strength for the panel. Results are displayed immediately. Using the system, a mill operator can adjust resin/wood proportion, reduce setup time and waste, produce internal bonds of a consistent quality and automatically mark deficient products.

  12. Water's Hydrogen Bond Strength

    CERN Document Server

    Chaplin, Martin

    2007-01-01

    Water is necessary both for the evolution of life and its continuance. It possesses particular properties that cannot be found in other materials and that are required for life-giving processes. These properties are brought about by the hydrogen bonded environment particularly evident in liquid water. Each liquid water molecule is involved in about four hydrogen bonds with strengths considerably less than covalent bonds but considerably greater than the natural thermal energy. These hydrogen bonds are roughly tetrahedrally arranged such that when strongly formed the local clustering expands, decreasing the density. Such low density structuring naturally occurs at low and supercooled temperatures and gives rise to many physical and chemical properties that evidence the particular uniqueness of liquid water. If aqueous hydrogen bonds were actually somewhat stronger then water would behave similar to a glass, whereas if they were weaker then water would be a gas and only exist as a liquid at sub-zero temperature...

  13. Upper Secondary Teachers' Knowledge for Teaching Chemical Bonding Models

    Science.gov (United States)

    Bergqvist, Anna; Drechsler, Michal; Rundgren, Shu-Nu Chang

    2016-01-01

    Researchers have shown a growing interest in science teachers' professional knowledge in recent decades. The article focuses on how chemistry teachers impart chemical bonding, one of the most important topics covered in upper secondary school chemistry courses. Chemical bonding is primarily taught using models, which are key for understanding science. However, many studies have determined that the use of models in science education can contribute to students' difficulties understanding the topic, and that students generally find chemical bonding a challenging topic. The aim of this study is to investigate teachers' knowledge of teaching chemical bonding. The study focuses on three essential components of pedagogical content knowledge (PCK): (1) the students' understanding, (2) representations, and (3) instructional strategies. We analyzed lesson plans about chemical bonding generated by 10 chemistry teachers with whom we also conducted semi-structured interviews about their teaching. Our results revealed that the teachers were generally unaware of how the representations of models they used affected student comprehension. The teachers had trouble specifying students' difficulties in understanding. Moreover, most of the instructional strategies described were generic and insufficient for promoting student understanding. Additionally, the teachers' rationale for choosing a specific representation or activity was seldom directed at addressing students' understanding. Our results indicate that both PCK components require improvement, and suggest that the two components should be connected. Implications for the professional development of pre-service and in-service teachers are discussed.

  14. The coordination chemistry of saturated molecules

    OpenAIRE

    Bercaw, John E.; Labinger, Jay A.

    2007-01-01

    Our understanding of bonding in transition metal complexes, as well as our ability to use that understanding in the synthesis and application of new species, has evolved over the last 100 years; and in some sense this special feature on the coordination chemistry of saturated molecules may be considered to represent its culmination. The nature of complexes between transition metal ions and neutral molecules such as ammonia was first correctly described by Werner around the beginning of the 20...

  15. Water-Chemistry and On-Site Sulfur-Speciation Data for Selected Springs in Yellowstone National Park, Wyoming, 1996-1998

    Science.gov (United States)

    Ball, James W.; Nordstrom, Kirk D.; McCleskey, R. Blaine; Schoonen, Martin A.A.; Xu, Yong

    2001-01-01

    Fifty-eight water analyses are reported for samples collected from 19 hot springs and their overflow drainages and one ambient-temperature acid stream in Yellowstone National Park (YNP) during 1996-98. These water samples were collected and analyzed as part of research investigations on microbially mediated sulfur oxidation in stream waters and sulfur redox speciation in hot springs in YNP and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. The research on sulfur redox speciation in hot springs is a collaboration with the State University of New York at Stony Brook, Northern Arizona University, and the U.S. Geological Survey (USGS). One ambient-temperature acidic stream system, Alluvium Creek and its tributaries in Brimstone Basin, was studied in detail. Analyses were performed adjacent to the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability and preservability of the constituent. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity and F were determined within a few days of sample collection by titration and by ion-selective electrode, respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Concentrations of Cl, SO4, and Br were determined by IC within a few days of sample collection. Concentrations of Fe(II) and Fe(total) were determined by ultraviolet/visible spectrophotometry within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li, Na, and K were determined by flame atomic absorption (Li) and emission (Na, K) spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), Mg, Mn, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace

  16. A Simple Visualization of Double Bond Properties: Chemical Reactivity and UV Fluorescence

    Science.gov (United States)

    Grayson, Scott M.

    2012-01-01

    A simple, easily visualized thin-layer chromatography (TLC) staining experiment is presented that highlights the difference in reactivity between aromatic double bonds and nonaromatic double bonds. Although the stability of aromatic systems is a major theme in organic chemistry, the concept is rarely reinforced "visually" in the undergraduate…

  17. Body of Knowledge (BOK) for Copper Wire Bonds

    Science.gov (United States)

    Rutkowski, E.; Sampson, M. J.

    2015-01-01

    Copper wire bonds have replaced gold wire bonds in the majority of commercial semiconductor devices for the latest technology nodes. Although economics has been the driving mechanism to lower semiconductor packaging costs for a savings of about 20% by replacing gold wire bonds with copper, copper also has materials property advantages over gold. When compared to gold, copper has approximately: 25% lower electrical resistivity, 30% higher thermal conductivity, 75% higher tensile strength and 45% higher modulus of elasticity. Copper wire bonds on aluminum bond pads are also more mechanically robust over time and elevated temperature due to the slower intermetallic formation rate - approximately 1/100th that of the gold to aluminum intermetallic formation rate. However, there are significant tradeoffs with copper wire bonding - copper has twice the hardness of gold which results in a narrower bonding manufacturing process window and requires that the semiconductor companies design more mechanically rigid bonding pads to prevent cratering to both the bond pad and underlying chip structure. Furthermore, copper is significantly more prone to corrosion issues. The semiconductor packaging industry has responded to this corrosion concern by creating a palladium coated copper bonding wire, which is more corrosion resistant than pure copper bonding wire. Also, the selection of the device molding compound is critical because use of environmentally friendly green compounds can result in internal CTE (Coefficient of Thermal Expansion) mismatches with the copper wire bonds that can eventually lead to device failures during thermal cycling. Despite the difficult problems associated with the changeover to copper bonding wire, there are billions of copper wire bonded devices delivered annually to customers. It is noteworthy that Texas Instruments announced in October of 2014 that they are shipping microcircuits containing copper wire bonds for safety critical automotive applications

  18. Polyoxometalate systems for the catalytic selective production of nonthermodynamic alkenes from alkanes. Nature of excited-state deactivation processes and control of subsequent thermal processes in polyoxometalate photoredox chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Renneke, R.F.; Pasquali, M.; Hill, C.L. (Emory Univ., Atlanta, GA (USA))

    1990-08-29

    The photooxidations of exemplary branched acyclic alkanes and cycloalkanes by a range of polyoxotungstates varying in charge density, ground-state redox potential, acidity, and other properties were examined in detail. The organic products generated in these reactions depend on the polyoxometalate used, and in particular on the ground-state redox potential of the complex. Under anaerobic conditions acyclic branched alkanes yield principally alkenes, while cycloalkanes yield principally alkenes and dimers. Alkyl methyl ketones, derived in part from reaction with acetonitrile solvent, and isomerized alkanes are produced with some alkane substrates. Under aerobic conditions, autoxidation, initiated by radicals generated in the photoinduced redox chemistry, is observed. Under aerobic conditions the polyoxotungstates with formal redox potentials more negative than {minus}1.0 V vs Ag/AgNO{sub 3}(CH{sub 3}CN), such as W{sub 10}O{sub 32}{sup 4{minus}} and W{sub 6}O{sub 19}{sup 2{minus}}, photochemically dehydrogenate branched acyclic alkanes in high selectivity to {alpha}-olefins and the least substituted alkenes, products heretofore undocumented in photooxidation reactions catalyzed by polyoxometalates.

  19. Beryllium chemistry and processing

    CERN Document Server

    Walsh, Kenneth A

    2009-01-01

    This book introduces beryllium; its history, its chemical, mechanical, and physical properties including nuclear properties. The 29 chapters include the mineralogy of beryllium and the preferred global sources of ore bodies. The identification and specifics of the industrial metallurgical processes used to form oxide from the ore and then metal from the oxide are thoroughly described. The special features of beryllium chemistry are introduced, including analytical chemical practices. Beryllium compounds of industrial interest are identified and discussed. Alloying, casting, powder processing, forming, metal removal, joining and other manufacturing processes are covered. The effect of composition and process on the mechanical and physical properties of beryllium alloys assists the reader in material selection. The physical metallurgy chapter brings conformity between chemical and physical metallurgical processing of beryllium, metal, alloys, and compounds. The environmental degradation of beryllium and its all...

  20. Bond strength of repaired amalgam restorations.

    Science.gov (United States)

    Rey, Rosalia; Mondragon, Eduardo; Shen, Chiayi

    2015-01-01

    This in vitro study investigated the interfacial flexural strength (FS) of amalgam repairs and the optimal combination of repair materials and mechanical retention required for a consistent and durable repair bond. Amalgam bricks were created, each with 1 end roughened to expose a fresh surface before repair. Four groups followed separate repair protocols: group 1, bonding agent with amalgam; group 2, bonding agent with composite resin; group 3, mechanical retention (slot) with amalgam; and group 4, slot with bonding agent and amalgam. Repaired specimens were stored in artificial saliva for 1, 10, 30, 120, or 360 days before being loaded to failure in a 3-point bending test. Statistical analysis showed significant changes in median FS over time in groups 2 and 4. The effect of the repair method on the FS values after each storage period was significant for most groups except the 30-day storage groups. Amalgam-amalgam repair with adequate condensation yielded the most consistent and durable bond. An amalgam bonding agent could be beneficial when firm condensation on the repair surface cannot be achieved or when tooth structure is involved. Composite resin can be a viable option for amalgam repair in an esthetically demanding region, but proper mechanical modification of the amalgam surface and selection of the proper bonding system are essential. PMID:26325656

  1. New physics and chemistry in high electrostatic fields

    Science.gov (United States)

    Karahka, M. L.; Kreuzer, H. J.

    2016-01-01

    Fields of the order of volts per meter exist along micron-sized tips. They are of the magnitude of fields inside atoms and molecules and can affect their electronic structure. This leads to a continuous periodic table resulting in new field-induced chemistry. We will present a tutorial treatment of this new physics and chemistry explaining such surprising phenomena like covalent bonding of helium to metal surfaces, metallization of semiconductors and insulators, and more.

  2. Constructing Models in Teaching of Chemical Bonds: Ionic Bond, Covalent Bond, Double and Triple Bonds, Hydrogen Bond and Molecular Geometry

    Science.gov (United States)

    Uce, Musa

    2015-01-01

    Studies in chemistry education show that chemistry topics are considered as abstract, complicated and hard to understand by students. For this reason, it is important to develop new materials and use them in classes for better understanding of abstract concepts. Moving from this point, a student-centered research guided by a teacher was conducted…

  3. Nuclear chemistry

    International Nuclear Information System (INIS)

    Topics covered include: mass asymmetry and total kinetic energy release in the spontaneous fission of 262105; calculation of spontaneous fission properties of very heavy nuclei - 98 less than or equal to Z less than or equal to 106 and 150 less than or equal to N less than or equal to 164; energy losses for 84Kr ions in nickel, aluminium and titanium; differences in compound nuclei formed with 40Ar and 84Kr projectiles; measurement of the energy division vs. mass in highly damped reactions; ambiguities in the inference of precompound emission from excitation function analysis; selective laser one-atom detection of neutral prompt fission fragments; laser induced nuclear polarization - application to the study of spontaneous fission isomers; quadrupole and hexadecapole deformations in the actinide nuclei; high-spin states in 164Yb; contrasting behavior of h/sub 9/2/ and i/sub 13/2/ bands in 185Au; multiple band crossings in 164Er; recoil-distance measurement of lifetimes of rotational states in 164Dy, lifetimes of ground-band states in 192Pt and 194Pt and application of the rotation-alignment model; coulomb excitation of vibrational nuclei with heavy ions; surface structure of deformed nuclei; valency contribution to neutron capture in 32S; neutron capture cross section of manganese; search for superheavy elements in natural samples by neutron multiplicity counting; and gamma-ray studies on the geochemistry of achondritic meteorites

  4. Electronic bond tuning with heterocyclic carbenes

    KAUST Repository

    Falivene, Laura

    2013-01-01

    We discuss the impact of the nature of the heterocyclic carbene ring, when used as a complex forming ligand, on the relative stability of key intermediates in three typical Ru, Pd and Au promoted reactions. Results show that P-heterocyclic carbenes have a propensity to increase the bonding of the labile ligand and of the substrate in Ru-promoted olefin metathesis, whereas negligible impact is expected on the stability of the ruthenacycle intermediate. In the case of Pd cross-coupling reactions, dissociation of a P-heterocyclic carbene is easier than dissociation of the N-heterocyclic analogue. In the case of the Au-OH synthon, the Au-OH bond is weakened with the P-heterocyclic carbene ligands. A detailed energy decomposition analysis is performed to rationalize these results. © 2013 The Royal Society of Chemistry.

  5. Selective Covalent Chemistry via Gas-Phase Ion/ion Reactions: An Exploration of the Energy Surfaces Associated with N-Hydroxysuccinimide Ester Reagents and Primary Amines and Guanidine Groups

    Science.gov (United States)

    Bu, Jiexun; Fisher, Christine M.; Gilbert, Joshua D.; Prentice, Boone M.; McLuckey, Scott A.

    2016-06-01

    Selective covalent bond forming reactions (referred to as covalent reactions) can occur in gas-phase ion/ion reactions and take place via the formation of a long-lived chemical complex. The gas-phase ion/ion reactivity between sulfo- N-hydroxysuccinimide (sulfo-NHS) ester reagent anions and peptide cations containing a primary amine or guanidine group has been examined via DFT calculations and complex dissociation rate measurements. The results reveal insights regarding the roles of the barriers of competing processes within the complex. When the covalent reaction is exothermic, two prototypical cases, determined by the nature of the energy surface, are apparent. The product partitioning between covalent reaction and simple proton transfer upon dissociation of the long-lived complex is sensitive to activation conditions when the transition state barrier for covalent reaction is relatively high ( case 1) but is insensitive to activation conditions when the transition state barrier is relatively low ( case 2). Covalent reaction efficiencies are very high in case 2 scenarios, such as when the reactive site is a guanidine and the anion attachment site is a guanidinium ion. Covalent reaction efficiencies are variable, and generally low, in case 1 scenarios, such as when an amine is the reactive site and an ammonium ion is the site of anion attachment. A relatively long slow-heating step prior to the complex dissociation step, however, can dramatically increase covalent reaction yield in case 1 scenarios.

  6. Green chemistry: A tool in Pharmaceutical Chemistry

    Directory of Open Access Journals (Sweden)

    Smita Talaviya

    2012-07-01

    Full Text Available Green chemistry expresses an area of research developing from scientific discoveries about pollution awareness and it utilizes a set of principles that reduces or eliminates the use or generation of hazardous substances in all steps of particular synthesis or process. Chemists and medicinal scientists can greatly reduce the risk to human health and the environment by following all the valuable principles of green chemistry. The most simple and direct way to apply green chemistry in pharmaceuticals is to utilize eco-friendly, non-hazardous, reproducible and efficient solvents and catalysts in synthesis of drug molecules, drug intermediates and in researches involving synthetic chemistry. Microwave synthesis is also an important tool of green chemistry by being an energy efficient process.

  7. Transversely Compressed Bonded Joints

    DEFF Research Database (Denmark)

    Hansen, Christian Skodborg; Schmidt, Jacob Wittrup; Stang, Henrik

    2012-01-01

    The load capacity of bonded joints can be increased if transverse pressure is applied at the interface. The transverse pressure is assumed to introduce a Coulomb-friction contribution to the cohesive law for the interface. Response and load capacity for a bonded single-lap joint was derived using...... non-linear fracture mechanics. The results indicated a good correlation between theory and tests. Furthermore, the model is suggested as theoretical base for determining load capacity of bonded anchorages with transverse pressure, in externally reinforced concrete structures....

  8. On the Nature of Bonding in Parallel Spins in Monovalent Metal Clusters.

    Science.gov (United States)

    Danovich, David; Shaik, Sason

    2016-05-27

    As we approach the Lewis model centennial, it may be timely to discuss novel bonding motifs. Accordingly, this review discusses no-pair ferromagnetic (NPFM) bonds that hold together monovalent metallic atoms using exclusively parallel spins. Thus, without any traditional electron-pair bonds, the bonding energy per atom in these clusters can reach 20 kcal mol(-1). This review describes the origins of NPFM bonding using a valence bond (VB) analysis, which shows that this bonding motif arises from bound triplet electron pairs that are delocalized over all the close neighbors of a given atom in the cluster. The VB model accounts for the tendency of NPFM clusters to assume polyhedral shapes with rather high symmetry and for the very steep rise of the bonding energy per atom. The advent of NPFM clusters offers new horizons in chemistry of highly magnetic species sensitive to magnetic and electric fields. PMID:27070320

  9. Environmental chemistry: Volume A

    Energy Technology Data Exchange (ETDEWEB)

    Yen, T.F.

    1999-08-01

    This is an extensive introduction to environmental chemistry for engineering and chemical professionals. The contents of Volume A include a brief review of basic chemistry prior to coverage of litho, atmo, hydro, pedo, and biospheres.

  10. CHINESE JOURNAL OF CHEMISTRY

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    @@Chinese Journal of Chemistry is an international journal published in English by the Chinese Chemical Society with its editorial office hosted by Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences.

  11. Supramolecular chemistry of cucurbiturils

    International Nuclear Information System (INIS)

    The main principles of the design of supramolecular compounds starting from organic macrocyclic cavitands, viz., cucurbit[n]urils [C6H6N4O2]n (n=5-10), are considered. The presence of the hydrophobic inner cavity along with polar carbonyl groups forming the cucurbituril portals are responsible for high specificity of the formation of host-guest complexes. The unique ability of cucurbiturils to act as synthetic molecular containers is discussed. In these containers, bimolecular reactions between specially selected guests proceed with high regio- and stereoselectivity. The review surveys new data on the directed construction of supramolecular organic-inorganic compounds through the formation of an extensive network of hydrogen bonds between the portal oxygen atoms of cucurbiturils and water molecules of metal aqua complexes. The bibliography includes 108 references.

  12. Hydrogen bonds in methane-water clusters.

    Science.gov (United States)

    Salazar-Cano, Juan-Ramón; Guevara-García, Alfredo; Vargas, Rubicelia; Restrepo, Albeiro; Garza, Jorge

    2016-08-24

    Characterization of hydrogen bonds in CH4-(H2O)12 clusters was carried out by using several quantum chemistry tools. An initial stochastic search provided around 2 500 000 candidate structures, then, using a convex-hull polygon criterion followed by gradient based optimization under the Kohn-Sham scheme, a total of 54 well defined local minima were located in the Potential Energy Surface. These structures were further analyzed through second-order many-body perturbation theory with an extended basis set at the MP2/6-311++G(d,p) level. Our analysis of Gibbs energies at several temperatures clearly suggests a structural preference toward compact water clusters interacting with the external methane molecule, instead of the more commonly known clathrate-like structures. This study shows that CH4-(H2O)12 clusters may be detected at temperatures up to 179 K, this finding provides strong support to a recently postulated hypothesis that suggests that methane-water clusters could be present in Mars at these conditions. Interestingly, we found that water to water hydrogen bonding is strengthened in the mixed clusters when compared to the isolated water dimer, which in turn leads to a weakening of the methane to water hydrogen bonding when compared to the CH4-(H2O) dimer. Finally, our evidence places a stern warning about the abilities of popular geometrical criteria to determine the existence of hydrogen bonds. PMID:27492605

  13. Progress in Kdo-glycoside chemistry

    Science.gov (United States)

    Kosma, Paul

    2016-01-01

    Glycosylation chemistry of 3-deoxy-D-manno-oct-2-ulosonic acid units has been considerably developed within the last decade. This review covers major achievements with respect to improved yields and anomeric selectivity as well as suppression of the elimination side reaction via selection of dedicated protecting groups and appropriate activation of the anomeric center. PMID:27274586

  14. Green Chemistry and Education.

    Science.gov (United States)

    Hjeresen, Dennis L.; Schutt, David L.; Boese, Janet M.

    2000-01-01

    Many students today are profoundly interested in the sustainability of their world. Introduces Green Chemistry and its principles with teaching materials. Green Chemistry is the use of chemistry for pollution prevention and the design of chemical products and processes that are environmentally benign. (ASK)

  15. Electrochemical activation of a tetrathiafulvalene halogen bond donor in solution.

    Science.gov (United States)

    Oliveira, R; Groni, S; Fave, C; Branca, M; Mavré, F; Lorcy, D; Fourmigué, M; Schöllhorn, B

    2016-06-21

    The halogen bond donor properties of iodo-tetrathiafulvalene (I-TTF) can be electrochemically switched and controlled via reversible oxidation in the solution phase. Interestingly the activation of only one single halogen bond yielded already a strong and selective interaction, quantified by cyclic voltammetry. The standard potentials of the redox couples I-TTF(0/1+) and I-TTF(1+/2+) were observed to shift upon the addition of halides. These anions selectively stabilize the cationic I-TTF species through halogen bonding in polar liquid electrolytes. The thermodynamic affinity constants for chloride and bromide binding to the oxidized species have been determined. Competition in halide binding between I-TTF(1+) and other halogen bond donors allowed for comparing the relative donor strength of the respective electrophilic species. Furthermore it has been shown that halogen bonding can prevail over hydrogen bonding in the investigated system. PMID:27231819

  16. Computational Chemistry Comparison and Benchmark Database

    Science.gov (United States)

    SRD 101 NIST Computational Chemistry Comparison and Benchmark Database (Web, free access)   The NIST Computational Chemistry Comparison and Benchmark Database is a collection of experimental and ab initio thermochemical properties for a selected set of molecules. The goals are to provide a benchmark set of molecules for the evaluation of ab initio computational methods and allow the comparison between different ab initio computational methods for the prediction of thermochemical properties.

  17. Activation of C-H and B-H bonds through agostic bonding: an ELF/QTAIM insight.

    Science.gov (United States)

    Zins, Emilie-Laure; Silvi, Bernard; Alikhani, M Esmaïl

    2015-04-14

    Agostic bonding is of paramount importance in C-H bond activation processes. The reactivity of the σ C-H bond thus activated will depend on the nature of the metallic center, the nature of the ligand involved in the interaction and co-ligands, as well as on geometric parameters. Because of their importance in organometallic chemistry, a qualitative classification of agostic bonding could be very much helpful. Herein we propose descriptors of the agostic character of bonding based on the electron localization function (ELF) and Quantum Theory of Atoms in Molecules (QTAIM) topological analysis. A set of 31 metallic complexes taken, or derived, from the literature was chosen to illustrate our methodology. First, some criteria should prove that an interaction between a metallic center and a σ X-H bond can indeed be described as "agostic" bonding. Then, the contribution of the metallic center in the protonated agostic basin, in the ELF topological description, may be used to evaluate the agostic character of bonding. A σ X-H bond is in agostic interaction with a metal center when the protonated X-H basin is a trisynaptic basin with a metal contribution strictly larger than the numerical uncertainty, i.e. 0.01 e. In addition, it was shown that the weakening of the electron density at the X-Hagostic bond critical point with respect to that of X-Hfree well correlates with the lengthening of the agostic X-H bond distance as well as with the shift of the vibrational frequency associated with the νX-H stretching mode. Furthermore, the use of a normalized parameter that takes into account the total population of the protonated basin, allows the comparison of the agostic character of bonding involved in different complexes. PMID:25760795

  18. Handbook of wafer bonding

    CERN Document Server

    Ramm, Peter; Taklo, Maaike M V

    2011-01-01

    Written by an author and editor team from microsystems companies and industry-near research organizations, this handbook and reference presents dependable, first-hand information on bonding technologies.In the first part, researchers from companies and institutions around the world discuss the most reliable and reproducible technologies for the production of bonded wafers. The second part is devoted to current and emerging applications, including microresonators, biosensors and precise measuring devices.

  19. Surface chemistry essentials

    CERN Document Server

    Birdi, K S

    2013-01-01

    Surface chemistry plays an important role in everyday life, as the basis for many phenomena as well as technological applications. Common examples range from soap bubbles, foam, and raindrops to cosmetics, paint, adhesives, and pharmaceuticals. Additional areas that rely on surface chemistry include modern nanotechnology, medical diagnostics, and drug delivery. There is extensive literature on this subject, but most chemistry books only devote one or two chapters to it. Surface Chemistry Essentials fills a need for a reference that brings together the fundamental aspects of surface chemistry w

  20. The New Color of Chemistry: Green Chemistry

    Directory of Open Access Journals (Sweden)

    Zuhal GERÇEK

    2012-01-01

    Full Text Available Green chemistry which is the new application of chemistry rules provides solutions to problems that mankind is faced with climate changes, sustainable agriculture, energy, toxics, depletion of natural sources e.g. designing new chemicals and processes that production and utilization of hazardous matters. So, it is the indispensible tool for sustainable development. Current and future chemists should consider the human health and ecological issues in their professional life. In order to provide a solution for this requirement, green chemistry rules and under standings should be primarily taken in the university curriculum and at all educational levels.

  1. Annual report 1984 Chemistry Department

    International Nuclear Information System (INIS)

    This report contains a brief survey of the main activities in the Chemistry Department. All articles and reports published and lectures given in 1984 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry , environmental chemistry, polymer chemistry, geochemistry and waste disposal, radical chemistry, positron annihilation, mineral processing, and general. (author)

  2. Orbital entanglement in quantum chemistry

    CERN Document Server

    Boguslawski, Katharina

    2014-01-01

    The basic concepts of orbital entanglement and its application to chemistry are briefly reviewed. The calculation of orbital entanglement measures from correlated wavefunctions is discussed in terms of reduced $n$-particle density matrices. Possible simplifications in their evaluation are highlighted in case of seniority-zero wavefunctions. Specifically, orbital entanglement allows us to dissect electron correlation effects in its strong and weak contributions, to determine bond orders, to assess the quality and stability of active space calculations, to monitor chemical reactions, and to identify points along the reaction coordinate where electronic wavefunctions change drastically. Thus, orbital entanglement represents a useful and intuitive tool to interpret complex electronic wavefunctions and to facilitate a qualitative understanding of electronic structure and how it changes in chemical processes.

  3. Control of Reactivity and Regioselectivity for On-Surface Dehydrogenative Aryl-Aryl Bond Formation.

    Science.gov (United States)

    Kocić, Nemanja; Liu, Xunshan; Chen, Songjie; Decurtins, Silvio; Krejčí, Ondřej; Jelínek, Pavel; Repp, Jascha; Liu, Shi-Xia

    2016-05-01

    Regioselectivity is of fundamental importance in chemical synthesis. Although many concepts for site-selective reactions are well established for solution chemistry, it is not a priori clear whether they can easily be transferred to reactions taking place on a metal surface. A metal will fix the chemical potential of the electrons and perturb the electronic states of the reactants because of hybridization. Additionally, techniques to characterize chemical reactions in solution are generally not applicable to on-surface reactions. Only recent developments in resolving chemical structures by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) paved the way for identifying individual reaction products on surfaces. Here we exploit a combined STM/AFM technique to demonstrate the on-surface formation of complex molecular architectures built up from a heteroaromatic precursor, the tetracyclic pyrazino[2,3-f][4,7]phenanthroline (pap) molecule. Selective intermolecular aryl-aryl coupling via dehydrogenative C-H activation occurs on Au(111) upon thermal annealing under ultrahigh vacuum (UHV) conditions. A full atomistic description of the different reaction products based on an unambiguous discrimination between pyrazine and pyridine moieties is presented. Our work not only elucidates that ortho-hydrogen atoms of the pyrazine rings are preferentially activated over their pyridine equivalents, but also sheds new light onto the participation of substrate atoms in metal-organic coordination bonding during covalent C-C bond formation. PMID:27059121

  4. Selective Organic and Organometallic Reactions in Water-Soluble Host-Guest Supramolecular Systems

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael D.; Raymond, Kenneth N.; Bergman, Robert G.

    2008-02-16

    Inspired by the efficiency and selectivity of enzymes, synthetic chemists have designed and prepared a wide range of host molecules that can bind smaller molecules with their cavities; this area has become known as 'supramolecular' or 'host-guest' chemistry. Pioneered by Lehn, Cram, Pedersen, and Breslow, and followed up by a large number of more recent investigators, it has been found that the chemical environment in each assembly - defined by the size, shape, charge, and functional group availability - greatly influences the guest-binding characteristics of these compounds. In contrast to the large number of binding studies that have been carried out in this area, the exploration of chemistry - especially catalytic chemistry - that can take place inside supramolecular host cavities is still in its infancy. For example, until the work described here was carried out, very few examples of organometallic reactivity inside supramolecular hosts were known, especially in water solution. For that reason, our group and the group directed by Kenneth Raymond decided to take advantage of our complementary expertise and attempt to carry out metal-mediated C-H bond activation reactions in water-soluble supramolecular systems. This article begins by providing background from the Raymond group in supramolecular coordination chemistry and the Bergman group in C-H bond activation. It goes on to report the results of our combined efforts in supramolecular C-H activation reactions, followed by extensions of this work into a wider range of intracavity transformations.

  5. Dilemmas in zirconia bonding: A review

    Directory of Open Access Journals (Sweden)

    Obradović-Đuričić Kosovka

    2013-01-01

    Full Text Available This article presents a literature review on the resin bond to zirconia ceramic. Modern esthetic dentistry has highly recognized zirconia, among other ceramic materials. Biocompatibility of zirconia, chemical and dimensional stability, excellent mechanical properties, all together could guarantee optimal therapeutical results in complex prosthodontic reconstruction. On the other hand, low thermal degradation, aging of zirconia as well as problematic bonding of zirconia framework to dental luting cements and tooth structures, opened the room for discussion concerning their clinical durability. The well known methods of mechanical and chemical bonding used on glass-ceramics are not applicable for use with zirconia. Therefore, under critical clinical situations, selection of the bonding mechanism should be focused on two important points: high initial bond strength value and long term bond strength between zirconia-resin interface. Also, this paper emphases the use of phosphate monomer luting cements on freshly air-abraded zirconia as the simplest and most effective way for zirconia cementation procedure today.

  6. Thioamides: versatile bonds to induce directional and cooperative hydrogen bonding in supramolecular polymers.

    Science.gov (United States)

    Mes, Tristan; Cantekin, Seda; Balkenende, Dirk W R; Frissen, Martijn M M; Gillissen, Martijn A J; De Waal, Bas F M; Voets, Ilja K; Meijer, E W; Palmans, Anja R A

    2013-06-24

    The amide bond is a versatile functional group and its directional hydrogen-bonding capabilities are widely applied in, for example, supramolecular chemistry. The potential of the thioamide bond, in contrast, is virtually unexplored as a structuring moiety in hydrogen-bonding-based self-assembling systems. We report herein the synthesis and characterisation of a new self-assembling motif comprising thioamides to induce directional hydrogen bonding. N,N',N''-Trialkylbenzene-1,3,5-tris(carbothioamide)s (thioBTAs) with either achiral or chiral side-chains have been readily obtained by treating their amide-based precursors with P2S5. The thioBTAs showed thermotropic liquid crystalline behaviour and a columnar mesophase was assigned. IR spectroscopy revealed that strong, three-fold, intermolecular hydrogen-bonding interactions stabilise the columnar structures. In apolar alkane solutions, thioBTAs self-assemble into one-dimensional, helical supramolecular polymers stabilised by three-fold hydrogen bonding. Concentration- and temperature-dependent self-assembly studies performed by using a combination of UV and CD spectroscopy demonstrated a cooperative supramolecular polymerisation mechanism and a strong amplification of supramolecular chirality. The high dipole moment of the thioamide bond in combination with the anisotropic shape of the resulting cylindrical aggregate gives rise to sufficiently strong depolarised light scattering to enable depolarised dynamic light scattering (DDLS) experiments in dilute alkane solution. The rotational and translational diffusion coefficients, D(trans) and D(rot), were obtained from the DDLS measurements, and the average length, L, and diameter, d, of the thioBTA aggregates were derived (L = 490 nm and d = 3.6 nm). These measured values are in good agreement with the value L(w) = 755 nm obtained from fitting the temperature-dependent CD data by using a recently developed equilibrium model. This experimental verification

  7. The New Color of Chemistry: Green Chemistry

    OpenAIRE

    GERÇEK, Zuhal

    2012-01-01

    Green chemistry which is the new application of chemistry rules provides solutions to problems that mankind is faced with climate changes, sustainable agriculture, energy, toxics, depletion of natural sources e.g. designing new chemicals and processes that production and utilization of hazardous matters. So, it is the indispensible tool for sustainable development. Current and future chemists should consider the human health and ecological issues in their professional life. In order to provid...

  8. Philosophy of Chemistry or Philosophy with Chemistry?

    OpenAIRE

    Bernadette Bensaude-Vincent

    2014-01-01

    Chemistry deserves more philosophical attention not so much to do justice to a long-neglected science or to enhance its cultural prestige, but to undermine a number of taken-for-granted assumptions about scientific rationality and more importantly to diversify our metaphysical views of nature and reality. In brief, this paper does not make the case for a philosophy of chemistry. It rather urges philosophers of science to listen to chemists and discuss what they learn from them. Because over t...

  9. A Bidenate Amide Bonded Stationary Phase for HPLC

    Institute of Scientific and Technical Information of China (English)

    Yan Shun MA; Yuan De LONG; Yong Liang DING; Tian Bao HUANG

    2003-01-01

    A novel bonded stationary phase, bidenate amide bonded stationary phase (BABSP), was prepared by reacting YWG silica gel firstly with 3-aminopropyltrimethoxysilane, then with diacid chloride. Hydrophobicity, selectivity, and especially silanophilic activity of BABSP were evaluated. The stationary phase exhibited good column efficiency and peak shape for separation of some basic solutes.

  10. Innovations in bonding to zirconia-based materials: Part I

    NARCIS (Netherlands)

    M.N.M. Abou Shelib; J.P. Matinlinna; Z. Salameh; H. Ounsi

    2008-01-01

    Abstract Objectives Establishing a reliable bond to zirconia-based materials has proven to be difficult which is the major limitation against fabricating adhesive zirconia restorations. This bond could be improved using novel selective infiltration etching conditioning in combination with engineered

  11. Bonding to zirconia using a new surface treatment

    NARCIS (Netherlands)

    M.N. Aboushelib; A.J. Feilzer; C.J. Kleverlaan

    2010-01-01

    Purpose: Selective infiltration etching (SIE) is a newly developed surface treatment used to modify the surface of zirconia-based materials, rendering them ready for bonding to resin cements. The aim of this study was to evaluate the zirconia/resin bond strength and durability using the proposed tec

  12. 2011 Organometallic Chemistry (July 10-15, 2011, Salve Regina University, Newport, RI)

    Energy Technology Data Exchange (ETDEWEB)

    Dr. Emilio Bunel

    2011-07-15

    Organometallic chemistry has played and will continue to play a significant role in helping us understand the way bonds are made or broken in the presence of a transition metal complex. Current challenges range from the efficient exploitation of energy resources to the creative use of natural and artificial enzymes. Most of the new advances in the area are due to our extended understanding of processes at a molecular level due to new mechanistic studies, techniques to detect reaction intermediates and theory. The conference will bring the most recent advances in the field including nanocatalysis, surface organometallic chemistry, characterization techniques, new chemical reactivity and theoretical approaches along with applications to organic synthesis and the discovery of new materials. The Conference will bring together a collection of investigators who are at the forefront of their field, and will provide opportunities for junior scientists and graduate students to present their work in poster format and exchange ideas with leaders in the field. Six outstanding posters will be selected for short talks. The collegial atmosphere of this Conference, with programmed discussion sessions as well as opportunities for informal gatherings in the afternoons and evenings, provides an avenue for scientists from different disciplines to brainstorm and promotes cross-disciplinary collaborations in the various research areas represented. Graduate students and postdoctoral fellows should also consider participating in the Gordon Research Seminar on Organometallic Chemistry (July 9-10, same location) which is specially designed to promote interaction and discussion between junior scientists.

  13. Romanian government bond market

    Directory of Open Access Journals (Sweden)

    Cornelia POP

    2012-12-01

    Full Text Available The present paper aims to present the level of development reached by Romanian government bond market segment, as part of the country financial market. The analysis will be descriptive (the data series available for Romania are short, based on the secondary data offered by the official bodies involved in the process of issuing and trading the Romanian government bonds (Romanian Ministry of Public Finance, Romanian National Bank and Bucharest Stock Exchange, and also on secondary data provided by the Federation of European Stock Exchanges.To enhance the market credibility as a benchmark, a various combination of measures is necessary; among these measures are mentioned: the extension of the yield curve; the issuance calendars in order to improve transparency; increasing the disclosure of information on public debt issuance and statistics; holding regular meetings with dealers, institutional investors and rating agencies; introducing a system of primary dealers; establishing a repurchase (repo market in the government bond market. These measures will be discussed based on the evolution presented inside the paper.The paper conclude with the fact that, until now, the Romanian government bond market did not provide a benchmark for the domestic financial market and that further efforts are needed in order to increase the government bond market transparency and liquidity.

  14. Overview on the history of organofluorine chemistry from the viewpoint of material industry

    OpenAIRE

    Okazoe, Takashi

    2009-01-01

    Fluorine (from “le fluor”, meaning “to flow”) is a second row element of Group 17 in the periodic table. When bound to carbon it forms the strongest bond in organic chemistry to give organofluorine compounds. The scientific field treating them, organofluorine chemistry, started before elemental fluorine itself was isolated. Applying the fruits in academia, industrial organofluorine chemistry has developed over 80 years via dramatic changes during World War II. Nowadays, it provides various ma...

  15. The open-close mechanism of M2 channel protein in influenza A virus:A computational study on the hydrogen bonds and cation-π interactions among His37 and Trp41

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    The M2 protein from influenza A virus is a tetrameric ion channel. It was reported that the permeation of the ion channel is correlated with the hydrogen bond network among His37 residues and the cation-π interactions between His37 and Trp41. In the present study,the hydrogen bonding network of 4-methyl-imidazoles was built to mimic the hydrogen bonds between His37 residues,and the cation-π interactions between 4-methyl-imidazolium and indole systems were selected to represent the interac-tions between His37 and Trp41. Then,quantum chemistry calculations at the MP2/6-311G level were carried out to explore the properties of the hydrogen bonds and the cation-π interactions. The calcula-tion results indicate that the binding strength of the N-H···N hydrogen bond between imidazole rings is up to -6.22 kcal·mol-1,and the binding strength of the strongest cation-π interaction is up to -18.8 kcal·mol-1(T-shaped interaction) or -12.3 kcal·mol-1(parallel stacking interaction). Thus,the calcu-lated binding energies indicate that it is possible to control the permeation of the M2 ion channel through the hydrogen bond network and the cation-π interactions by altering the pH values.

  16. The open-close mechanism of M2 channel protein in influenza A virus: A computational study on the hydrogen bonds and cation-π interactions among His37 and Trp41

    Institute of Scientific and Technical Information of China (English)

    CHENG JiaGao; ZHU WeiLiang; WANG YanLi; YAN XiuHua; LI Zhong; TANG Yun; JIANG HuaLiang

    2008-01-01

    The M2 protein from influenza A virus is a tetrameric ion channel. It was reported that the permeation of the ion channel is correlated with the hydrogen bond network among His37 residues and the cation-π interactions between His37 and Trp41. In the present study, the hydrogen bonding network of 4-methyl-imidazoles was built to mimic the hydrogen bonds between His37 residues, and the cation-π interactions between 4-methyl-imidazolium and indole systems were selected to represent the interac-tions between His37 and Trp41. Then, quantum chemistry calculations at the MP2/6-311G** level were carried out to explore the properties of the hydrogen bonds and the cation-π interactions. The calculation results indicate that the binding strength of the N--H…N hydrogen bond between imidazole rings is up to -6.22 kcal·mol-1, and the binding strength of the strongest cation-π interaction is up to -18.8 kcal·mol-1 (T-shaped interaction) or -12.3 kcal·mol-1 (parallel stacking interaction). Thus, the calculated binding energies indicate that it is possible to control the permeation of the M2 ion channel through the hydrogen bond network and the cation-π interactions by altering the pH values.

  17. Bioinorganic Chemistry Modeled with the TPSSh Density Functional

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2008-01-01

    In this work, the TPSSh density functional has been benchmarked against a test set of experimental structures and bond energies for 80 transition-metal-containing diatomics. It is found that the TPSSh functional gives structures of the same quality as other commonly used hybrid and nonhybrid...... promising density functional for use and further development within the field of bioinorganic chemistry....

  18. Insulation bonding test system

    Science.gov (United States)

    Beggs, J. M.; Johnston, G. D.; Coleman, A. D.; Portwood, J. N.; Saunders, J. M.; Redmon, J. W.; Porter, A. C. (Inventor)

    1984-01-01

    A method and a system for testing the bonding of foam insulation attached to metal is described. The system involves the use of an impacter which has a calibrated load cell mounted on a plunger and a hammer head mounted on the end of the plunger. When the impacter strikes the insulation at a point to be tested, the load cell measures the force of the impact and the precise time interval during which the hammer head is in contact with the insulation. This information is transmitted as an electrical signal to a load cell amplifier where the signal is conditioned and then transmitted to a fast Fourier transform (FFT) analyzer. The FFT analyzer produces energy spectral density curves which are displayed on a video screen. The termination frequency of the energy spectral density curve may be compared with a predetermined empirical scale to determine whether a igh quality bond, good bond, or debond is present at the point of impact.

  19. Multilayered film microreactors fabricated by a one-step thermal bonding technique with high reproducibility and their applications.

    Science.gov (United States)

    Min, Kyoung-Ik; Kim, Jin-Oh; Kim, Heejin; Im, Do Jin; Kim, Dong-Pyo

    2016-03-21

    We report the versatile uses of multilayered polyimide (PI) film microreactors with various functions including pressure tolerance, three-dimensional mixing and multistep membrane emulsification. Such PI film microreactors were fabricated by a simple one-step thermal bonding technique with high reproducibility. Upon bonding at 300 °C for 1 hour, the thin and flexible film microdevices could withstand pressure up to 8.6 MPa and 16.3 MPa with PI adhesive film or fluoropolymer adhesive, respectively, due to differences in wettability. The hydrophilic and hydrophobic microchannel devices were used to generate monodisperse oil-in-water (O/W) and water-in-oil (W/O) droplets, and polymer micro/nanoparticles at a high generation frequency. A monolithic and chemical resistant film microreactor with a three-dimensional serpentine microchannel was used for the selective reduction of ester to aldehyde by efficient mixing and quenching in a flash chemistry manner, within a several 10(1) millisecond time scale. Furthermore, a novel multilayered film microreactor for organic-aqueous biphasic interfacial reactions was devised by embedding a membrane layer to induce chaotic mixing in both the interface and emulsified phase by flowing through multiple numbers of meshed structures along the hydrophobic channel. This simple and economic fabrication technique significantly facilitates mass production of multilayered film devices that could be useful as a platform for various microfluidic applications in chemistry and biology. PMID:26886679

  20. Multilayered film microreactors fabricated by a one-step thermal bonding technique with high reproducibility and their applications.

    Science.gov (United States)

    Min, Kyoung-Ik; Kim, Jin-Oh; Kim, Heejin; Im, Do Jin; Kim, Dong-Pyo

    2016-03-21

    We report the versatile uses of multilayered polyimide (PI) film microreactors with various functions including pressure tolerance, three-dimensional mixing and multistep membrane emulsification. Such PI film microreactors were fabricated by a simple one-step thermal bonding technique with high reproducibility. Upon bonding at 300 °C for 1 hour, the thin and flexible film microdevices could withstand pressure up to 8.6 MPa and 16.3 MPa with PI adhesive film or fluoropolymer adhesive, respectively, due to differences in wettability. The hydrophilic and hydrophobic microchannel devices were used to generate monodisperse oil-in-water (O/W) and water-in-oil (W/O) droplets, and polymer micro/nanoparticles at a high generation frequency. A monolithic and chemical resistant film microreactor with a three-dimensional serpentine microchannel was used for the selective reduction of ester to aldehyde by efficient mixing and quenching in a flash chemistry manner, within a several 10(1) millisecond time scale. Furthermore, a novel multilayered film microreactor for organic-aqueous biphasic interfacial reactions was devised by embedding a membrane layer to induce chaotic mixing in both the interface and emulsified phase by flowing through multiple numbers of meshed structures along the hydrophobic channel. This simple and economic fabrication technique significantly facilitates mass production of multilayered film devices that could be useful as a platform for various microfluidic applications in chemistry and biology.

  1. The Illiquidity of Corporate Bonds

    OpenAIRE

    Bao, Jack; Pan, Jun; Wang, Jiang

    2011-01-01

    This paper examines the illiquidity of corporate bonds and its asset-pricing implications. Using transactions data from 2003 to 2009, we show that the illiquidity in corporate bonds is substantial, significantly greater than what can be explained by bid–ask spreads. We establish a strong link between bond illiquidity and bond prices. In aggregate, changes in market-level illiquidity explain a substantial part of the time variation in yield spreads of high-rated (AAA through A) bonds, overshad...

  2. Improved machine learning method for analysis of gas phase chemistry of peptides

    Directory of Open Access Journals (Sweden)

    Ahn Natalie

    2008-12-01

    Full Text Available Abstract Background Accurate peptide identification is important to high-throughput proteomics analyses that use mass spectrometry. Search programs compare fragmentation spectra (MS/MS of peptides from complex digests with theoretically derived spectra from a database of protein sequences. Improved discrimination is achieved with theoretical spectra that are based on simulating gas phase chemistry of the peptides, but the limited understanding of those processes affects the accuracy of predictions from theoretical spectra. Results We employed a robust data mining strategy using new feature annotation functions of MAE software, which revealed under-prediction of the frequency of occurrence in fragmentation of the second peptide bond. We applied methods of exploratory data analysis to pre-process the information in the MS/MS spectra, including data normalization and attribute selection, to reduce the attributes to a smaller, less correlated set for machine learning studies. We then compared our rule building machine learning program, DataSqueezer, with commonly used association rules and decision tree algorithms. All used machine learning algorithms produced similar results that were consistent with expected properties for a second gas phase mechanism at the second peptide bond. Conclusion The results provide compelling evidence that we have identified underlying chemical properties in the data that suggest the existence of an additional gas phase mechanism for the second peptide bond. Thus, the methods described in this study provide a valuable approach for analyses of this kind in the future.

  3. Chemistry and morphology of coal liquefaction. Annual report, October 1, 1984-September 30, 1985

    Energy Technology Data Exchange (ETDEWEB)

    Heinemann, H.; Fish, R.H.

    1985-09-01

    The removal of nitrogen from complex matrices such as coal liquids is an extremely important area to study. We recently discovered that polynuclear heteroaromatic nitrogen compounds can be selectively reduced only in the nitrogen containing ring. We now wish to focus on the aspects of carbon-nitrogen cleavage in the saturated nitrogen heterocyclic ring of model coal compounds in order to better understand how nitrogen can be removed without additional substantial use of hydrogen gas for that reaction to occur. A duel approach will be followed that will provide fundamental information on the cleavage of carbon-nitrogen bonds using metal complexes of rhenium, iridium and ruthenium. The important coordination of metal complexes to saturated nitrogen compounds followed by oxidative addition to a methylene group alpha to the nitrogen atom will allow formation of metalla-azacyclopropanes and dimetalla-azacyclobutenes. These compounds will be reacted with nucleophiles to hopefully afford carbon-nitrogen bond cleavage. The compounds will also be reacted under hydrogenation conditions to provide a similar carbon-nitrogen bond cleavage reaction. The second approach, carried out simultaneously, will use various bulk metals such as nickel, rhodium and ruthenium supported on silica and alumina with 1,2,3,4-tetrahydroquinoline as the substrate and at temperatures of approx.300/sup 0/C and 1 atm H/sub 2/ gas to provide HDN chemistry under mild experimental conditions.

  4. The Trouble With Bonds

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    @@ In early June,global financial markets gyrated downwards in the wake of central banks'tough language on inflation.At one point bond prices reflected expectations of four rate hikes by the US Federal Reserve (Fed) in the next 12 months.As a result,the dollar firmed,oil prices stabilized,and yield curves flattened around the world.If all these inflation-fighting measures are real,the situation bodes well for bonds.But,I think otherwise.

  5. Programming Surface Chemistry with Engineered Cells.

    Science.gov (United States)

    Zhang, Ruihua; Heyde, Keith C; Scott, Felicia Y; Paek, Sung-Ho; Ruder, Warren C

    2016-09-16

    We have developed synthetic gene networks that enable engineered cells to selectively program surface chemistry. E. coli were engineered to upregulate biotin synthase, and therefore biotin synthesis, upon biochemical induction. Additionally, two different functionalized surfaces were developed that utilized binding between biotin and streptavidin to regulate enzyme assembly on programmable surfaces. When combined, the interactions between engineered cells and surfaces demonstrated that synthetic biology can be used to engineer cells that selectively control and modify molecular assembly by exploiting surface chemistry. Our system is highly modular and has the potential to influence fields ranging from tissue engineering to drug development and delivery.

  6. Applications of the Cambridge Structural Database in organic chemistry and crystal chemistry.

    Science.gov (United States)

    Allen, Frank H; Motherwell, W D Samuel

    2002-06-01

    The Cambridge Structural Database (CSD) and its associated software systems have formed the basis for more than 800 research applications in structural chemistry, crystallography and the life sciences. Relevant references, dating from the mid-1970s, and brief synopses of these papers are collected in a database, DBUse, which is freely available via the CCDC website. This database has been used to review research applications of the CSD in organic chemistry, including supramolecular applications, and in organic crystal chemistry. The review concentrates on applications that have been published since 1990 and covers a wide range of topics, including structure correlation, conformational analysis, hydrogen bonding and other intermolecular interactions, studies of crystal packing, extended structural motifs, crystal engineering and polymorphism, and crystal structure prediction. Applications of CSD information in studies of crystal structure precision, the determination of crystal structures from powder diffraction data, together with applications in chemical informatics, are also discussed.

  7. A Protein Data Bank survey reveals shortening of intermolecular hydrogen bonds in ligand-protein complexes when a halogenated ligand is an H-bond donor.

    Directory of Open Access Journals (Sweden)

    Jarosław Poznański

    Full Text Available Halogen bonding in ligand-protein complexes is currently widely exploited, e.g. in drug design or supramolecular chemistry. But little attention has been directed to other effects that may result from replacement of a hydrogen by a strongly electronegative halogen. Analysis of almost 30000 hydrogen bonds between protein and ligand demonstrates that the length of a hydrogen bond depends on the type of donor-acceptor pair. Interestingly, lengths of hydrogen bonds between a protein and a halogenated ligand are visibly shorter than those estimated for the same family of proteins in complexes with non-halogenated ligands. Taking into account the effect of halogenation on hydrogen bonding is thus important when evaluating structural and/or energetic parameters of ligand-protein complexes. All these observations are consistent with the concept that halogenation increases the acidity of the proximal amino/imino/hydroxyl groups and thus makes them better, i.e. stronger, H-bond donors.

  8. Seeking hydrogen bonds- with and without neutron diffraction

    International Nuclear Information System (INIS)

    The hydrogen-bond interaction can be studied using a variety of spectroscopic and crystallographic techniques, as well as theoretical studies based on quantum chemical principles, semi-empirical procedures, and statistical interpretations. A degree of specificity, along with flexibility, provides H-bonded systems with a variety of unusual and interesting physical, chemical and biological properties. Neutron diffraction is the method of choice for obtaining high-precision data on hydrogen-atom positions and hydrogen-bond stereo-chemistry in crystals. Neutron inelastic scattering can provide information on the dynamics of H-bonded systems. High-precision neutron diffraction studies on a variety of crystal hydrates, amino acids and small peptides, development of semi-empirical potential functions for bent-hydrogen bonds, and statistical analysis of H-bond populations associated with various donor and acceptor groups are some of the investigations on hydrogen bonding, carried out at Trombay during the past three decades. (author). 39 refs., 7 figs., 3 tabs

  9. Journal of Business Chemistry

    OpenAIRE

    2013-01-01

    The Journal of Business Chemistry examines issues associated with leadership and management for chemists and managers working in chemical research or industry. This journal is devoted to improving and developing the field of Business Chemistry. The Journal of Business Chemistry publishes peer-reviewed papers (including case studies) and essays. Areas for possible publication in include: leadership issues in the chemical and biochemical industry, such as teamwork, team building, mentoring, coa...

  10. Mathematical Thinking in Chemistry

    OpenAIRE

    José L. Villaveces; Guillermo Restrepo

    2012-01-01

    Mathematical chemistry is often thought to be a 20th-century subdiscipline of chemistry, but in this paper we discuss several early chemical ideas and some landmarks of chemistry as instances of the mathematical way of thinking; many of them before 1900. By the mathematical way of thinking, we follow Weyl's description of it in terms of functional thinking, i.e. setting up variables, symbolizing them, and seeking for functions relating them. The cases we discuss are Plato's triangles, Geoffro...

  11. Orbital interactions in chemistry

    CERN Document Server

    Albright, Thomas A; Whangbo, Myung-Hwan

    2013-01-01

    Explains the underlying structure that unites all disciplines in chemistry Now in its second edition, this book explores organic, organometallic, inorganic, solid state, and materials chemistry, demonstrating how common molecular orbital situations arise throughout the whole chemical spectrum. The authors explore the relationships that enable readers to grasp the theory that underlies and connects traditional fields of study within chemistry, thereby providing a conceptual framework with which to think about chemical structure and reactivity problems. Orbital Interactions

  12. Interfacial chemistry of zinc anodes for reinforced concrete structures

    Energy Technology Data Exchange (ETDEWEB)

    Covino, B.S. Jr.; Bullard, S.J.; Cramer, S.D.; Holcomb, G.R. [Dept. of Energy, Albany, OR (United States). Albany Research Center; McGill, G.E.; Cryer, C.B. [Oregon Dept. of Transportation, Salem, OR (United States); Stoneman, A. [International Lead Zinc Research Organization, Research Triangle Park, NC (United States); Carter, R.R. [California Dept. of Transportation, Sacramento, CA (United States)

    1997-12-01

    Thermally-sprayed zinc anodes are used in both galvanic and impressed current cathodic protection systems for reinforced concrete structures. The Albany Research Center, in collaboration with the Oregon Department of Transportation, has been studying the effect of electrochemical aging on the bond strength of zinc anodes for bridge cathodic protection systems. Changes in anode bond strength and other anode properties can be explained by the chemistry of the zinc-concrete interface. The chemistry of the zinc-concrete interface in laboratory electrochemical aging studies is compared with that of several bridges with thermal-sprayed zinc anodes and which have been in service for 5 to 10 years using both galvanic and impressed current cathodic protection systems. The bridges are the Cape Creek Bridge on the Oregon coast and the East Camino Undercrossing near Placerville, CA. Also reported are interfacial chemistry results for galvanized steel rebar from the 48 year old Longbird Bridge in Bermuda.

  13. Shear bond strength, failure modes, and confocal microscopy of bonded amalgam restorations.

    Science.gov (United States)

    Cianconi, Luigi; Conte, Gabriele; Mancini, Manuele

    2011-01-01

    This study evaluated the shear bond strength, failure modes, and confocal microscopy of two different amalgam alloy restorations lined with five adhesive systems. Two regular-set high-copper dental amalgam alloys, Amalcap Plus and Valiant Ph.D, and five commercially available adhesive systems were selected. One hundred and twenty freshly-extracted human third molars were used for the study. The results were statistically evaluated using two-factor analysis of variance (ANOVA). The shear bond strength (SBS) of amalgam to dentin was significantly affected by both the adhesive (pValiant Ph.D, 31 of 50 exhibited adhesive failure, and 19 displayed mixed failure. Laser optical microscopy (OM) of the bonded interface revealed the presence of a good hybrid layer was evident in all experimental groups. Higher bond strengths were measured for four of the five adhesives when used in combination with the spherical alloy. PMID:21383518

  14. Functionalization of Mechanochemically Passivated Germanium Nanoparticles via "Click" Chemistry

    Science.gov (United States)

    Purkait, Tapas Kumar

    Germanium nanoparticles (Ge NPs) may be fascinating for their electronic and optoelectronic properties, as the band gap of Ge NPs can be tuned from the infrared into the visible range of solar spectru. Further functionalization of those nanoparticles may potentially lead to numerous applications ranging from surface attachment, bioimaging, drug delivery and nanoparticles based devices. Blue luminescent germanium nanoparticles were synthesized from a novel top-down mechanochemical process using high energy ball milling (HEBM) of bulk germanium. Various reactive organic molecules (such as, alkynes, nitriles, azides) were used in this process to react with fresh surface and passivate the surface through Ge-C or Ge-N bond. Various purification process, such as gel permeation chromatography (GPC), Soxhlet dailysis etc. were introduced to purify nanoparticles from molecular impurities. A size separation technique was developed using GPC. The size separated Ge NPs were characterize by TEM, small angle X-ray scattering (SAXS), UV-vis absorption and photoluminescence (PL) emission spectroscopy to investigate their size selective properties. Germanium nanoparticles with alkyne termini group were prepared by HEBM of germanium with a mixture of n-alkynes and alpha, o-diynes. Additional functionalization of those nanoparticles was achieved by copper(I) catalyzed azide-alkyne "click" reaction. A variety of organic and organometallic azides including biologically important glucals have been reacted in this manner resulting in nanopartilces adorned with ferrocenyl, trimethylsilyl, and glucal groups. Additional functionalization of those nanoparticles was achieved by reactions with various azides via a Cu(I) catalyzed azide-alkyne "click" reaction. Various azides, including PEG derivatives and cylcodextrin moiety, were grafted to the initially formed surface. Globular nanoparticle arrays were formed through interparticle linking via "click" chemistry or "host-guest" chemistry

  15. The Chemistry Institute

    OpenAIRE

    Fontecave, Marc

    2015-01-01

    Chemistry at the Collège de France has received particular attention over the last few years. After the departures of Profs Jean-Marie Lehn and Jacques Livage, new ambition for developing this discipline has led to the creation of several Chairs: Prof. Marc Fontecave’s Chair of Chemistry of Biological Processes in 2008, Prof. Clément Sanchez’ Chair of Chemistry of Hybrid Materials in 2011, and the Chair of Chemistry of Materials and Energy, which Prof. Jean-Marie Tarascon has held since 2014....

  16. Group theory and chemistry

    CERN Document Server

    Bishop, David M

    1993-01-01

    Group theoretical principles are an integral part of modern chemistry. Not only do they help account for a wide variety of chemical phenomena, they simplify quantum chemical calculations. Indeed, knowledge of their application to chemical problems is essential for students of chemistry. This complete, self-contained study, written for advanced undergraduate-level and graduate-level chemistry students, clearly and concisely introduces the subject of group theory and demonstrates its application to chemical problems.To assist chemistry students with the mathematics involved, Professor Bishop ha

  17. DOE fundamentals handbook: Chemistry

    International Nuclear Information System (INIS)

    This handbook was developed to assist nuclear facility operating contractors in providing operators, maintenance personnel, and the technical staff with the necessary fundamentals training to ensure a basic understanding of chemistry. This volume contains the following modules: reactor water chemistry (effects of radiation on water chemistry, chemistry parameters), principles of water treatment (purpose; treatment processes [ion exchange]; dissolved gases, suspended solids, and pH control; water purity), and hazards of chemicals and gases (corrosives [acids, alkalies], toxic compounds, compressed gases, flammable/combustible liquids)

  18. Advances in quantum chemistry

    CERN Document Server

    Sabin, John R

    2013-01-01

    Advances in Quantum Chemistry presents surveys of current topics in this rapidly developing field that has emerged at the cross section of the historically established areas of mathematics, physics, chemistry, and biology. It features detailed reviews written by leading international researchers. This volume focuses on the theory of heavy ion physics in medicine.Advances in Quantum Chemistry presents surveys of current topics in this rapidly developing field that has emerged at the cross section of the historically established areas of mathematics, physics, chemistry, and biology. It features

  19. Science Update: Analytical Chemistry.

    Science.gov (United States)

    Worthy, Ward

    1980-01-01

    Briefly discusses new instrumentation in the field of analytical chemistry. Advances in liquid chromatography, photoacoustic spectroscopy, the use of lasers, and mass spectrometry are also discussed. (CS)

  20. Cavity partition and functionalization of a [2+3] organic molecular cage by inserting polar P[double bond, length as m-dash]O bonds.

    Science.gov (United States)

    Feng, Genfeng; Liu, Wei; Peng, Yuxin; Zhao, Bo; Huang, Wei; Dai, Yafei

    2016-07-28

    The cavity of a [2+3] organic molecular cage was partitioned and functionalized by inserting inner-directed P[double bond, length as m-dash]O bonds, which shows CO2 capture and CH4 exclusion due to the size-matching and polarity effects. Computational results demonstrate that the successful segmentation via polar P[double bond, length as m-dash]O bonds facilitates the CO2 molecules to reside selectively inside the cavity. PMID:27356151

  1. Microbial cleavage of organic C-S bonds

    Science.gov (United States)

    Kilbane, II, John J.

    1994-01-01

    A microbial process for selective cleavage of organic C--S bonds which may be used for reducing the sulfur content of sulfur-containing organic carbonaceous materials, Microorganisms of Rhodococcus rhodochrous and Bacillus sphaericus have been found which have the ability of selective cleavage of organic C--S bonds. Particularly preferred microorganisms are Rhodococcus rhodochrous strain ATCC 53968 and Bacillus sphaericus strain ATCC 53969 and their derivatives.

  2. Validity of bond strength tests: A critical review: Part I.

    Science.gov (United States)

    Sirisha, Kantheti; Rambabu, Tankonda; Shankar, Yalavarthi Ravi; Ravikumar, Pabbati

    2014-07-01

    Adhesive systems are selected based on their bond strengths achieved while testing in laboratories. These bond strengths can predict the longevity of a restoration to some extent. There were several discrepancies in the reported bond strengths. To critically review the reliability of macro-bond strength tests used to evaluate resin-tooth interface. Relevant literature published between January 1983 and May 2013 was collected from PubMed database, Google scholar, and hand-searched journals of Conservative Dentistry, Endodontics and Dental materials. Variables that influence the test outcome are categorized into substrate-related factors, factors related to specimen properties, preparation of specimens, and test methodology. Impact of these variables on the test outcome is critically analyzed. There is lack of a standard format for reporting the bond strength tests, which could lead to misinterpretation of the data and bonding abilities of adhesives. PMID:25125840

  3. Photochemical tissue bonding

    Science.gov (United States)

    Redmond, Robert W.; Kochevar, Irene E.

    2012-01-10

    Photochemical tissue bonding methods include the application of a photosensitizer to a tissue and/or tissue graft, followed by irradiation with electromagnetic energy to produce a tissue seal. The methods are useful for tissue adhesion, such as in wound closure, tissue grafting, skin grafting, musculoskeletal tissue repair, ligament or tendon repair and corneal repair.

  4. Thread bonds in molecules

    CERN Document Server

    Ivlev, B

    2015-01-01

    Unusual chemical bonds are proposed. Each bond is almost covalent but is characterized by the thread of a small radius $\\sim 0.6\\times 10^{-11}$cm, between two nuclei in a molecule. The main electron density is concentrated outside the thread as in a covalent bond. The thread is formed by the electron wave function which has a tendency to be singular on it. The singularity along the thread is cut off by electron "vibrations" due to the interaction with zero point electromagnetic oscillations. The electron energy has its typical value of (1-10)eV. Due to the small tread radius the uncertainty of the electron momentum inside the thread is large resulting in a large electron kinetic energy $\\sim 1 MeV$. This energy is compensated by formation of a potential well due to the reduction of the energy of electromagnetic zero point oscillations. This is similar to formation of a negative van der Waals potential. Thread bonds are stable and cannot be created or destructed in chemical or optical processes.

  5. Open access and medicinal chemistry

    OpenAIRE

    Swain Chris

    2007-01-01

    Abstract Chemistry Central is a new open access website for chemists publishing peer-reviewed research in chemistry from a range of open access journals. A new addition, Chemistry Central Journal, will cover all of chemistry and will be broken down into discipline-specific sections, and Im delighted that Medicinal Chemistry will be a key discipline in this new journal.

  6. Annual report 1988 Chemistry Department

    International Nuclear Information System (INIS)

    This report contains a brief survey of the main activities in the Chemistry Department. The names and abstracts of all articles and reports published and lectures given in 1988 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry, environmental chemistry, polymer chemistry, chemical reactivity, mineral processing, and general. (author)

  7. Annual report 1989 Chemistry Department

    International Nuclear Information System (INIS)

    This report contains a brief survey of the main activities in the Chemistry Department. The names and abstracts of all articles and reports published and lectures given in 1989 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry, environmental chemistry, polymer chemistry, chemical reactivity, mineral processing, and general. (author)

  8. Annual report 1986 chemistry department

    International Nuclear Information System (INIS)

    This report contains a brief survey of the main activities in the Chemistry Department. All articles and reports published and lectures given in 1986 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry, environmental chemistry, polymer chemistry, radical chemistral, mineral processing, and general. (author)

  9. Students' Interdisciplinary Reasoning about "High-Energy Bonds" and ATP

    OpenAIRE

    Dreyfus, Benjamin W.; Geller, Benjamin D.; Sawtelle, Vashti; Svoboda, Julia; Turpen, Chandra; Redish, Edward F.

    2012-01-01

    Students' sometimes contradictory ideas about ATP (adenosine triphosphate) and the nature of chemical bonds have been studied in the biology and chemistry education literatures, but these topics are rarely part of the introductory physics curriculum. We present qualitative data from an introductory physics course for undergraduate biology majors that seeks to build greater interdisciplinary coherence and therefore includes these topics. In these data, students grapple with the apparent contra...

  10. Convertible bond valuation focusing on Chinese convertible bond market

    OpenAIRE

    Yang, Ke

    2010-01-01

    This paper mainly discusses the methods of valuation of convertible bonds in Chinese market. Different from common convertible bonds in European market, considering the complicate features of Chinese convertible bond, this paper represents specific pricing approaches for pricing convertible bonds with different provisions along with the increment of complexity of these provisions. More specifically, this paper represents the decomposing method and binomial tree method for pricing both of Non-...

  11. Linking Urban Air Pollution to Global Tropospheric Chemistry and Climate

    Science.gov (United States)

    Wang, Chien

    2005-01-01

    The two major tasks of this project are to study: (a) the impact of urban nonlinear chemistry on chemical budgets of key pollutants in non-urban areas; and (b) the influence of air pollution control strategies in selected metropolitan areas, particularly of emerging economies in East and South Asia, on tropospheric chemistry and hence on regional and global climate.

  12. The origin of life and the prebiotic chemistry

    OpenAIRE

    Dimas Augusto Morozin Zaia

    2004-01-01

    In the present paper, a historical view from Oparin-Haldane hypothesis to prebiotic chemistry is discussed. Several aspects of prebiotic chemistry are also discussed such as: environments where the abiotic synthesis of biomolecules and biopolymers could be occurred, primitive metabolism and genetic code, selection of L-amino acids and panspermia.

  13. Physical Chemistry of Molecular

    Institute of Scientific and Technical Information of China (English)

    2011-01-01

    @@ Established in 2009, the group consists of six researchers and more than 70 research assistants and graduate students from the CAS Key Laboratory of Molecular Nanostructures and Nanotechnologies at the CAS Institute of Chemistry.Its research focuses on the physical chemistry involved in molecular assembly, molecular nanostructures, functional nanomaterials and conceptual nano-devices.

  14. Chemistry in Microfluidic Channels

    Science.gov (United States)

    Chia, Matthew C.; Sweeney, Christina M.; Odom, Teri W.

    2011-01-01

    General chemistry introduces principles such as acid-base chemistry, mixing, and precipitation that are usually demonstrated in bulk solutions. In this laboratory experiment, we describe how chemical reactions can be performed in a microfluidic channel to show advanced concepts such as laminar fluid flow and controlled precipitation. Three sets of…

  15. The Breath of Chemistry

    DEFF Research Database (Denmark)

    Josephsen, Jens

    The present preliminary text is a short thematic presentation in biological inorganic chemistry meant to illustrate general and inorganic (especially coordination) chemistry in biochemistry. The emphasis is on molecular models to explain features of the complicated mechanisms essential to breathing...

  16. Career Options in Chemistry.

    Science.gov (United States)

    Belloli, Robert C.

    1985-01-01

    Describes a credit/no credit course which focuses on career options in chemistry. The course (consisting of 15 one-hour seminar-type sessions) includes guest speakers for several sessions and an emphasis (in introductory sessions) on graduate school in chemistry, the chemical industry, resumes, and interviews. Also briefly describes an internship…

  17. Chemistry of americium

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, W.W.

    1976-01-01

    Essential features of the descriptive chemistry of americium are reviewed. Chapter titles are: discovery, atomic and nuclear properties, collateral reading, production and uses, chemistry in aqueous solution, metal, alloys, and compounds, and, recovery, separation, purification. Author and subject indexes are included. (JCB)

  18. Indirect bonding technique in orthodontics

    Directory of Open Access Journals (Sweden)

    Kübra Yıldırım

    2016-08-01

    Full Text Available ‘Direct Bonding Technique’ which allows the fixed orthodontic appliances to be directly bonded to teeth without using bands decreased the clinic time for bracket bonding and increased esthetics and oral hygiene during orthodontic treatment. However, mistakes in bracket positioning were observed due to decreased direct visual sight and access to posterior teeth. ‘Indirect Bonding Technique’ was developed for eliminating these problems. Initially, decreased bond strength, higher bond failure rate, periodontal tissue irritation, compromised oral hygiene and increased laboratory time were the main disadvantages of this technique when compared to direct bonding. The newly developed materials and modified techniques help to eliminate these negative consequences. Today, the brackets bonded with indirect technique have similar bond strength with brackets bonded directly. Moreover, indirect and direct bonding techniques have similar effects on periodontal tissues. However, indirect bonding technique requires more attention and precision in laboratory and clinical stage, and has higher cost. Orthodontist's preference between these two bonding techniques may differ according to time spent in laboratory and clinic, cost, patient comfort and personal opinion.

  19. Areva's water chemistry guidebook with chemistry guidelines for next generation plants (AREVA EPRTM reactors)

    International Nuclear Information System (INIS)

    Over the years, AREVA globally has maintained a strong expertise in LWR water chemistry and has been focused on minimizing short-term and long-term detrimental effects of chemistry for startup, operation and shutdown chemistry for all key plant components (material integrity and reliability, promote optimal thermal performances, etc.) and fuel. Also AREVA is focused on minimizing contamination and equipment/plant dose rates. Current Industry Guidelines (EPRI, VGB, etc.) provide utilities with selected chemistry guidance for the current operating fleet. With the next generation of PWR plants (e.g. AREVA's EPRTM reactor), materials of construction and design have been optimized based on industry lessons learned over the last 50+ years. To support the next generation design, AREVA water chemistry experts, have subsequently developed a Chemistry Guidebook with chemistry guidelines based on an analysis of the current international practices, plant operating experience, R and D data and calculation codes now available and/or developed by AREVA. The AREVA LWR chemistry Guidebook can be used to help resolve utility and safety authority questions and addresses regulation requirement questions/issues for next generation plants. The Chemistry Guidebook provides water chemistry guidelines for primary coolant, secondary side circuit and auxiliary systems during startup, normal operation and shutdown conditions. It also includes conditioning and impurity limits, along with monitoring locations and frequency requirements. The Chemistry Guidebook Guidelines will be used as a design reference for AREVA's next generation plants (e.g. EPRTM reactor). (authors)

  20. Chemistry and materials science research report

    Energy Technology Data Exchange (ETDEWEB)

    1990-05-31

    The research reported here in summary form was conducted under the auspices of Weapons-Supporting Research (WSR) and Institutional Research and Development (IR D). The period covered is the first half of FY90. The results reported here are for work in progress; thus, they may be preliminary, fragmentary, or incomplete. Research in the following areas are briefly described: energetic materials, tritium, high-Tc superconductors, interfaces, adhesion, bonding, fundamental aspects of metal processing, plutonium, synchrotron-radiation-based materials science, photocatalysis on doped aerogels, laser-induced chemistry, laser-produced molecular plasmas, chemistry of defects, dta equipment development, electronic structure study of the thermodynamic and mechanical properties of Al-Li Alloys, and the structure-property link in sub-nanometer materials.

  1. 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.

  2. Mathematical Thinking in Chemistry

    Directory of Open Access Journals (Sweden)

    José L. Villaveces

    2012-05-01

    Full Text Available Mathematical chemistry is often thought to be a 20th-century subdiscipline of chemistry, but in this paper we discuss several early chemical ideas and some landmarks of chemistry as instances of the mathematical way of thinking; many of them before 1900. By the mathematical way of thinking, we follow Weyl's description of it in terms of functional thinking, i.e. setting up variables, symbolizing them, and seeking for functions relating them. The cases we discuss are Plato's triangles, Geoffroy's affinity table, Lavoisier's classification of substances and their relationships, Mendeleev's periodic table, Cayley's enumeration of alkanes, Sylvester's association of algebra and chemistry, and Wiener's relationship between molecular structure and boiling points. These examples show that mathematical chemistry has much more than a century of history.

  3. System approach to chemistry course

    OpenAIRE

    Lorina E. Kruglova; Valentina G. Derendyaeva

    2010-01-01

    The article considers the raise of chemistry profile for engineers and constructors training, discloses the system approach to chemistry course and singles out the most important modules from the course of general chemistry for construction industry.

  4. Bonding and charge transfer in nitrogen-donor uranyl complexes: insights from NEXAFS spectra.

    Science.gov (United States)

    Pemmaraju, C D; Copping, Roy; Wang, Shuao; Janousch, Markus; Teat, Simon J; Tyliszcak, Tolek; Canning, Andrew; Shuh, David K; Prendergast, David

    2014-11-01

    We investigate the electronic structure of three newly synthesized nitrogen-donor uranyl complexes [(UO2)(H2bbp)Cl2], [(UO)2(Hbbp)(Py)Cl], and [(UO2)(bbp)(Py)2] using a combination of near-edge X-ray absorption fine structure (NEXAFS) spectroscopy experiments and simulations. The complexes studied feature derivatives of the tunable tridentate N-donor ligand 2,6-bis(2-benzimidazyl)pyridine (bbp) and exhibit discrete chemical differences in uranyl coordination. The sensitivity of the N K-edge X-ray absorption spectrum to local bonding and charge transfer is exploited to systematically investigate the evolution of structural as well as electronic properties across the three complexes. A thorough interpretation of the measured experimental spectra is achieved via ab initio NEXAFS simulations based on the eXcited electron and Core-Hole (XCH) approach and enables the assignment of spectral features to electronic transitions on specific absorbing sites. We find that ligand-uranyl bonding leads to a signature blue shift in the N K-edge absorption onset, resulting from charge displacement toward the uranyl, while changes in the equatorial coordination shell of the uranyl lead to more subtle modulations in the spectral features. Theoretical simulations show that the flexible local chemistry at the nonbinding imidazole-N sites of the bbp ligand is also reflected in the NEXAFS spectra and highlights potential synthesis strategies to improve selectivity. In particular, we find that interactions of the bbp ligand with solvent molecules can lead to changes in ligand-uranyl binding geometry while also modulating the K-edge absorption. Our results suggest that NEXAFS spectroscopy combined with first-principles interpretation can offer insights into the coordination chemistry of analogous functionalized conjugated ligands. PMID:25330350

  5. Korean Kimchi Chemistry: A Multicultural Chemistry Connection

    Science.gov (United States)

    Murfin, Brian

    2009-01-01

    Connecting science with different cultures is one way to interest students in science, to relate science to their lives, and at the same time to broaden their horizons in a variety of ways. In the lesson described here, students make kimchi, a delicious and popular Korean dish that can be used to explore many important chemistry concepts,…

  6. China-Russia Bond

    Institute of Scientific and Technical Information of China (English)

    Ji Zhiye; Ma Zongshi

    2007-01-01

    @@ Thanks to China's successful launching of the Year of Russia, 2006 will surely go down as a milestone in the history of the China-Russia bond. Furthermore, a still-warmer climate will continue to prevail in 2007 when Moscow, in its turn, hosts the Year of China, trying to outshine its next-door neighbor in this regard, as Russian President Vladimir Putin promised in the exchange of new year greetings with his Chinese counterpart, President Hu Jintao.

  7. Annual report 1987 Chemistry Department

    International Nuclear Information System (INIS)

    This report contains a brief survey of the main activities in the Chemistry Department. The names and abstracts of all articles and reports published and lectures given in 1987 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, analytical- and organic chemistry, environmental chemistry, polymer chemistry, radical chemistry, mineral processing, and general. 13 ills., (author)

  8. Annual report 1982 chemistry department

    International Nuclear Information System (INIS)

    The work going on in the Risoe National Laboratory, Chemistry Department is briefly surveyed by a presentation of all articles and reports published in 1982. The facilities and equipment are barely mentioned. The papers are divided into eight activities: 1. neutron activation analysis 2. analytical- and organic chemistry 3. environmental chemistry 4. polymer chemistry 5. geochemistry 6. radical chemistry 7. poitron annihilation 8. uranium process chemistry. (author)

  9. Making Chemistry Relevant to the Engineering Major

    Science.gov (United States)

    Basu-Dutt, Sharmistha; Slappey, Charles; Bartley, Julie K.

    2010-01-01

    As part of a campus-wide, externally funded project to increase performance in, enthusiasm for, and retention within STEM disciplines, we developed an interdisciplinary, team-taught first-year seminar course. The construction and delivery of this course was designed to show the relevance of selected general chemistry topics such as matter and…

  10. Hydrated Cations in the General Chemistry Course.

    Science.gov (United States)

    Kauffman, George B.; Baxter, John F., Jr.

    1981-01-01

    Presents selected information regarding the descriptive chemistry of the common metal ions and their compounds, including the concepts of process of solution, polar molecules, ionic size and charge, complex ions, coordination number, and the Bronsted-Lowry acid-base theory. (CS)

  11. Development of HIP bonding procedure and mechanical properties of HIP bonded joints for reduced activation ferritic steel F-82H

    International Nuclear Information System (INIS)

    Structural materials of blanket components in fusion DEMO reactors will receive a neutron wall load more than 3-5MW/m2 as well as exposed by surface heat flux more than 0.5MW/m2. A reduced activation ferritic steel F-82H has been developed by JAERI in collaboration with NKK from viewpoints of resistance for high temperature and neutron loads and lower radioactivity. This study intends to obtain basic performance of F-82H to establish the fabrication procedure of the first wall and blanket box by using Hot Isostatic Pressing (HIP) bonding. Before HIP bonding tests, effects of heat treatment temperature and surface roughness on mechanical properties of joints were investigated in the heat treatment tests and diffusion bonding tests, respectively. From these results, the optimum HIP bonding conditions and the post heat treatment were selected. Using these conditions, the HIP bonding tests were carried out to evaluate HIP bondability and to obtain mechanical properties of the joints. Sufficient HIP bonding performance was obtained under the temperature of 1040degC, the compressive stress of 150MPa, the holding time of 2h, and the surface roughness ∼μ m. Mechanical properties of HIP bonded joints with these conditions were similar to those of as-received base metal. An oxide formation on the surface to be bonded would need to be avoided for sufficient bonding. The bonding ratio, Charpy impact value and fatigue performance of the joints strongly depended on the HIP conditions, especially temperature, while micro-structure, Vickers hardness and tensile properties had little dependence on the HIP temperature. The surface roughness strongly affected the bonding ratio and would be required to be in the level of a few μ m. In the HIP bonding test of the welded material, the once-melted surface could be jointed by the HIP bonding under the above-mentioned procedure. (J.P.N.)

  12. Annual Report 1984. Chemistry Department

    DEFF Research Database (Denmark)

    Funck, Jytte; Nielsen, Ole John

    This report contains a brief survey of the main activities in the Chemistry Department. All articles and reports published and lectures given in 1984 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry, an......, analytical- and organic chemistry, environmental chemistry, polymer chemistry, geochemistry and waste disposal, radical chemistry, positron annihilation, mineral processing, and general.......This report contains a brief survey of the main activities in the Chemistry Department. All articles and reports published and lectures given in 1984 are presented. The facilities and equipment are mentioned briefly. The activities are divided into the following groups: radioisotope chemistry...

  13. The coevolution of long-term pair bonds and cooperation.

    Science.gov (United States)

    Song, Z; Feldman, M W

    2013-05-01

    The evolution of social traits may not only depend on but also change the social structure of the population. In particular, the evolution of pairwise cooperation, such as biparental care, depends on the pair-matching distribution of the population, and the latter often emerges as a collective outcome of individual pair-bonding traits, which are also under selection. Here, we develop an analytical model and individual-based simulations to study the coevolution of long-term pair bonds and cooperation in parental care, where partners play a Snowdrift game in each breeding season. We illustrate that long-term pair bonds may coevolve with cooperation when bonding cost is below a threshold. As long-term pair bonds lead to assortative interactions through pair-matching dynamics, they may promote the prevalence of cooperation. In addition to the pay-off matrix of a single game, the evolutionarily stable equilibrium also depends on bonding cost and accidental divorce rate, and it is determined by a form of balancing selection because the benefit from pair-bond maintenance diminishes as the frequency of cooperators increases. Our findings highlight the importance of ecological factors affecting social bonding cost and stability in understanding the coevolution of social behaviour and social structures, which may lead to the diversity of biological social systems. PMID:23496797

  14. Coulombic Models in Chemical Bonding.

    Science.gov (United States)

    Sacks, Lawrence J.

    1986-01-01

    Compares the coulumbic point charge model for hydrogen chloride with the valence bond model. It is not possible to assign either a nonpolar or ionic canonical form of the valence bond model, while the covalent-ionic bond distribution does conform to the point charge model. (JM)

  15. Mittal bonded tongue thrusting appliance

    Directory of Open Access Journals (Sweden)

    Rekha Mittal

    2014-01-01

    Full Text Available These days majority of orthodontist includes bonded molar attachment in their inventory to eliminate the discomfort of molar separation during initial appointment and band spaces left at the end of treatment. This article describes a innovative and economical method of attachment of bonded tongue crib if required during the initial or later stages of treatment along with bonded molar tubes.

  16. Hamiltonian formulation of bond graphs

    NARCIS (Netherlands)

    Golo, Goran; Schaft, van der Arjan; Breedveld, Peter C.; Maschke, Bernhard M.; Johansson, R.; Rantzer, A.

    2003-01-01

    This paper deals with the mathematical formulation of bond graphs. It is proven that the power continuous part of bond graphs, the junction structure, can be associated with a Dirac structure and that the equations describing a bond graph model correspond to a port Hamiltonian system. The conditions

  17. Silicon clusters: Chemistry and structure

    Energy Technology Data Exchange (ETDEWEB)

    Jarrold, M.F.; Ray, U.; Ijiri, Y. (AT and T Bell Labs., Murray Hill, NJ (USA))

    1991-01-01

    The chemical reactions of size selected silicon cluster ions (containing up to 70 atoms) have been studied with a number of different reagents using injected ion drift tube techniques. Both kinetic and equilibrium measurements have been performed as a function of temperature, and the influence of cluster annealing on chemical reactivity explored. Unlike metal clusters, where bulk behavior appears to be approached with around 30 atoms, large silicon clusters (n up to 70) are much less reactive than bulk silicon surfaces. These results suggest that the clusters in the size range examined here are not small crystals of bulk silicon, but have compact, high coordination number structures with few dangling bonds. (orig.).

  18. Moderator Chemistry Program

    International Nuclear Information System (INIS)

    Over the past fifteen months, the Systems Chemistry Group of the Reactor Engineering Department has undertaken a comprehensive study of the Department's moderator chemistry program at Savannah River Site (SRS). An internal review was developed to formalize and document this program. Objectives were as outlined in a mission statement and action plan. In addition to the mission statement and action plan, nine separate task reports have been issued during the course of this study. Each of these task reports is included in this document as a chapter. This document is an organized compilation of the individual reports issued by the Systems Chemistry Group in assessment of SRS moderator chemistry to determine if there were significant gaps in the program as ft existed in October, 1989. While these reviews found no significant gaps in that mode of operation, or any items that adversely affected safety, items were identified that could be improved. Many of the items have already been dear with or are in the process of completion under this Moderator Chemistry Program and other Reactor Restart programs. A complete list of the items of improvement found under this assessment is found in Chapter 9, along with a proposed time table for correcting remaining items that can be improved for the chemistry program of SRS reactors. An additional external review of the moderator chemistry processes, recommendations, and responses to/from the Reactor Corrosion Mitigation Committee is included as Appendix to this compilation

  19. Moderator Chemistry Program

    Energy Technology Data Exchange (ETDEWEB)

    Dewitt, L.V.; Gibbs, A.; Lambert, D.P.; Bohrer, S.R.; Fanning, R.L.; Houston, M.W.; Stinson, S.L.; Deible, R.W.; Abdel-Khalik, S.I.

    1990-11-01

    Over the past fifteen months, the Systems Chemistry Group of the Reactor Engineering Department has undertaken a comprehensive study of the Department's moderator chemistry program at Savannah River Site (SRS). An internal review was developed to formalize and document this program. Objectives were as outlined in a mission statement and action plan. In addition to the mission statement and action plan, nine separate task reports have been issued during the course of this study. Each of these task reports is included in this document as a chapter. This document is an organized compilation of the individual reports issued by the Systems Chemistry Group in assessment of SRS moderator chemistry to determine if there were significant gaps in the program as ft existed in October, 1989. While these reviews found no significant gaps in that mode of operation, or any items that adversely affected safety, items were identified that could be improved. Many of the items have already been dear with or are in the process of completion under this Moderator Chemistry Program and other Reactor Restart programs. A complete list of the items of improvement found under this assessment is found in Chapter 9, along with a proposed time table for correcting remaining items that can be improved for the chemistry program of SRS reactors. An additional external review of the moderator chemistry processes, recommendations, and responses to/from the Reactor Corrosion Mitigation Committee is included as Appendix to this compilation.

  20. Moderator Chemistry Program

    Energy Technology Data Exchange (ETDEWEB)

    Dewitt, L.V.; Gibbs, A.; Lambert, D.P.; Bohrer, S.R.; Fanning, R.L.; Houston, M.W.; Stinson, S.L.; Deible, R.W.; Abdel-Khalik, S.I.

    1990-11-01

    Over the past fifteen months, the Systems Chemistry Group of the Reactor Engineering Department has undertaken a comprehensive study of the Department`s moderator chemistry program at Savannah River Site (SRS). An internal review was developed to formalize and document this program. Objectives were as outlined in a mission statement and action plan. In addition to the mission statement and action plan, nine separate task reports have been issued during the course of this study. Each of these task reports is included in this document as a chapter. This document is an organized compilation of the individual reports issued by the Systems Chemistry Group in assessment of SRS moderator chemistry to determine if there were significant gaps in the program as ft existed in October, 1989. While these reviews found no significant gaps in that mode of operation, or any items that adversely affected safety, items were identified that could be improved. Many of the items have already been dear with or are in the process of completion under this Moderator Chemistry Program and other Reactor Restart programs. A complete list of the items of improvement found under this assessment is found in Chapter 9, along with a proposed time table for correcting remaining items that can be improved for the chemistry program of SRS reactors. An additional external review of the moderator chemistry processes, recommendations, and responses to/from the Reactor Corrosion Mitigation Committee is included as Appendix to this compilation.

  1. Students' Interdisciplinary Reasoning about "High-Energy Bonds" and ATP

    CERN Document Server

    Dreyfus, Benjamin W; Sawtelle, Vashti; Svoboda, Julia; Turpen, Chandra; Redish, Edward F

    2012-01-01

    Students' sometimes contradictory ideas about ATP (adenosine triphosphate) and the nature of chemical bonds have been studied in the biology and chemistry education literatures, but these topics are rarely part of the introductory physics curriculum. We present qualitative data from an introductory physics course for undergraduate biology majors that seeks to build greater interdisciplinary coherence and therefore includes these topics. In these data, students grapple with the apparent contradiction between the energy released when the phosphate bond in ATP is broken and the idea that an energy input is required to break a bond. We see that students' perceptions of how each scientific discipline bounds the system of interest can influence how they justify their reasoning about a topic that crosses disciplines. This has consequences for a vision of interdisciplinary education that respects disciplinary perspectives while bringing them into interaction in ways that demonstrate consistency amongst the perspectiv...

  2. Developing and validating a chemical bonding instrument for Korean high school students

    Science.gov (United States)

    Jang, Nak Han

    The major purpose of this study was to develop a reliable and valid instrument designed to collect and investigate on Korean high school students' understanding about concepts regarding chemical bonding. The Chemical Bonding Diagnostic Test (CBDT) was developed by the procedure by previously relevant researches (Treagust, 1985; Peterson, 1986; Tan, 1994). The final instrument consisted of 15 two-tier items. The reliability coefficient (Cronbach alpha) for the whole test was 0.74. Also, the range of values for the discrimination index was from 0.38 to 0.90 and the overall average difficulty index was 0.38. The test was administered to 716 science declared students in Korean high school. The 37 common misconceptions on chemical bonding were identified through analysis of the items from the CBDT. The grade 11 students had slightly more misconceptions than the grade 12 students for ionic bonding, covalent bonding, and hydrogen bonding while the grade 12 students had more misconceptions about octet rule and hydrogen bonding than the grade 11 students. From the analysis of ANCOVA, there was no significant difference in grades, and between grade levels and gender on the mean score of CBDT. However, there was a significant difference in gender and a significant interaction between grade levels and chemistry preference. In conclusion, Korean high school students had the most common misconception about the electron configuration on ionic bonding and the water density on hydrogen bonding. Korean students' understanding about the chemical bonding was dependent on the interaction between grade levels and the chemistry preference. Consequently, grade 12 chemistry-preferred students had the highest mean scores among student groups concerned by this study.

  3. Magic, science and masculinity: marketing toy chemistry sets.

    Science.gov (United States)

    Al-Gailani, Salim

    2009-12-01

    At least since the late nineteenth century, toy chemistry sets have featured in standard scripts of the achievement of eminence in science, and they remain important in constructions of scientific identity. Using a selection of these toys manufactured in Britain and the United States, and with particular reference to the two dominant American brands, Gilbert and Chemcraft, this paper suggests that early twentieth-century chemistry sets were rooted in overlapping Victorian traditions of entertainment magic and scientific recreations. As chemistry set marketing copy gradually reoriented towards emphasising scientific modernity, citizenship, discipline and educational value, pre-twentieth-century traditions were subsumed within domestic-and specifically masculine-tropes. These developments in branding strategies point to transformations in both users' engagement with their chemistry sets and the role of scientific toys in domestic play. The chemistry set serves here as a useful tool for measuring cultural change and lay engagement with chemistry. PMID:20481190

  4. Pierre-Joseph Macquer: Chemistry in the French Enlightenment.

    Science.gov (United States)

    Lehman, Christine

    2014-01-01

    Despite recent studies of chemistry courses and of academic research at the beginning of the eighteenth century, the perception of chemistry in the French Enlightenment has often been overshadowed by Lavoisier's works. This article proposes three specific case studies selected from Pierre Joseph Macquer's (1718-84) rich career to show the continuous evolution of chemistry throughout the century: medicinal chemistry through the application of the Comte de La Garaye's metallic salt solutions, the emergence of industrial chemistry through a few of Macquer's evaluations at the Bureau du Commerce, and finally communal academic research through the experiments on diamonds using Tschirnhaus's lens. These examples attempt to illustrate the innovative, creative, dynamic, multicultural, and multifaceted chemistry of the Enlightenment.

  5. Experiments in physical chemistry

    CERN Document Server

    Wilson, J M; Denaro, A R

    1968-01-01

    Experiments in Physical Chemistry, Second Edition provides a compilation of experiments concerning physical chemistry. This book illustrates the link between the theory and practice of physical chemistry. Organized into three parts, this edition begins with an overview of those experiments that generally have a simple theoretical background. Part II contains experiments that are associated with more advanced theory or more developed techniques, or which require a greater degree of experimental skill. Part III consists of experiments that are in the nature of investigations wherein these invest

  6. Spatially Resolved Artificial Chemistry

    DEFF Research Database (Denmark)

    Fellermann, Harold

    2009-01-01

    Although spatial structures can play a crucial role in chemical systems and can drastically alter the outcome of reactions, the traditional framework of artificial chemistry is a well-stirred tank reactor with no spatial representation in mind. Advanced method development in physical chemistry has...... made a class of models accessible to the realms of artificial chemistry that represent reacting molecules in a coarse-grained fashion in continuous space. This chapter introduces the mathematical models of Brownian dynamics (BD) and dissipative particle dynamics (DPD) for molecular motion and reaction...

  7. Mathematics for physical chemistry

    CERN Document Server

    Mortimer, Robert G

    2013-01-01

    Mathematics for Physical Chemistry is the ideal supplementary text for practicing chemists and students who want to sharpen their mathematics skills while enrolled in general through physical chemistry courses. This book specifically emphasizes the use of mathematics in the context of physical chemistry, as opposed to being simply a mathematics text. This 4e includes new exercises in each chapter that provide practice in a technique immediately after discussion or example and encourage self-study. The early chapters are constructed around a sequence of mathematical topics, wit

  8. Chemistry of Covalent Organic Frameworks.

    Science.gov (United States)

    Waller, Peter J; Gándara, Felipe; Yaghi, Omar M

    2015-12-15

    Linking organic molecules by covalent bonds into extended solids typically generates amorphous, disordered materials. The ability to develop strategies for obtaining crystals of such solids is of interest because it opens the way for precise control of the geometry and functionality of the extended structure, and the stereochemical orientation of its constituents. Covalent organic frameworks (COFs) are a new class of porous covalent organic structures whose backbone is composed entirely of light elements (B, C, N, O, Si) that represent a successful demonstration of how crystalline materials of covalent solids can be achieved. COFs are made by combination of organic building units covalently linked into extended structures to make crystalline materials. The attainment of crystals is done by several techniques in which a balance is struck between the thermodynamic reversibility of the linking reactions and their kinetics. This success has led to the expansion of COF materials to include organic units linked by these strong covalent bonds: B-O, C-N, B-N, and B-O-Si. Since the organic constituents of COFs, when linked, do not undergo significant change in their overall geometry, it has been possible to predict the structures of the resulting COFs, and this advantage has facilitated their characterization using powder X-ray diffraction (PXRD) techniques. It has also allowed for the synthesis of COF structures by design and for their formation with the desired composition, pore size, and aperture. In practice, the modeled PXRD pattern for a given expected COF is compared with the experimental one, and depending on the quality of the match, this is used as a starting point for solving and then refining the crystal structure of the target COF. These characteristics make COFs an attractive class of new porous materials. Accordingly, they have been used as gas storage materials for energy applications, solid supports for catalysis, and optoelectronic devices. A large and

  9. 续建工程新旧混凝土框架节点粘钢和碳纤维加固方案比选%SCHEME COMPARISON AND SELECTION OF BONDING STEEL AND CFRP CONCRETE FRAME JOINT CONTINUED PROJECTS

    Institute of Scientific and Technical Information of China (English)

    李凯文

    2012-01-01

    In this thesis, some simple analytical FEA(finite element analysis) models are developed and utilized to determine the shear strain and seismic capacity of the frame joints of continued projects strengthened by two different methods, bonding steel and CFRP( carbon fiber reinforced plastic). The shear mechanism, failure mode, deformation capacity, bearing capacity and the reliability of the reinforced models and un-reinforced model are gathered to determine the influence produced by the reinforcements. Results of FEA show that both strengthening methods have significant influences on their failure capacity and seismic capacity. From some mechanical aspects, bonding steel proves more suitable for better engineering performance.%对续建工程中新旧混凝土交接处的框架梁柱节点进行抗震性能理论分析,对粘钢加固法及碳纤维加固法滞回曲线、骨架曲线、节点刚度、耗能能力和极限承载力进行了分析比较,得出一些结论:粘钢加固法抗剪承载能力增长较碳纤维加固法略大,粘钢加固法较碳纤维加固法对节点延性改善效果更为明显,两种方法加固后节点弹性和塑性阶段刚度均有明显提高,粘钢加固后的节点耗能能力增长显著而碳纤维加固后的节点耗能能力增长较弱。综合考虑以上方面后,工程节点加固应用粘钢加固法,工程效果较好。

  10. Vacuum ultraviolet photo-physical chemistry of hydrocarbon polymers

    Science.gov (United States)

    Truica-Marasescu, Florina-Elena

    The purpose of this study has been to investigate fundamental processes involved in the vacuum ultraviolet (VUV, lambda films at atmospheric pressure, thereby alleviating the need for expensive vacuum pumps and other auxiliary equipment necessary for continuous low-pressure plasma roll-to-roll treatment of flexible substrates. Another important advantage of VUV photochemistry over plasma is that more specific surface chemistries can be achieved with monochromatic VUV radiation, due to selective (photo-) chemistries both on the solid surface and in the gas phase. The hydrocarbon polymers used for this study were well-characterized low-density polyethylene, LDPE; biaxially-oriented polypropylene, BOPP; polystyrene, PS; and poly(methylmethacrylate), PMMA. Due to the complexity of interactions between VUV photons and polymers, especially when the latter are in a reactive gas, VUV-wavelength-dependent effects on the physico-chemical properties of irradiated polymer surfaces have been investigated under two different set of conditions, namely: VUV exposure in vacuum, and in a reactive atmosphere of low-pressure ammonia, VUV/NH3. In the former case, we investigated wavelength (lambda)-dependent material ablation ("etching") by in-situ quartz crystal microbalance (QCM) measurements, as a function of the irradiation dose, D. Near-surface structural changes (the creation of unsaturation, cross-linking, etc.) and radical-creation reactions resulting from VUV-initiated bond scissions were analysed by attenuated total reflectance infrared spectroscopy (ATR-FTIR) and by X-ray photoelectron spectroscopy (XPS) following irradiation. For all polymers studied the etch rates, R(lambda), were found to correlate well with the corresponding absorption coefficients, alpha(lambda), and with the accumulation rates, K, of various (C=C)-containing groups, determined from quantitative FTIR measurements. PMMA was found to have the highest R values, and the rate of mass loss of BOPP was higher

  11. ASEAN+3 Bond Market Guides

    OpenAIRE

    Asian Development Bank (ADB)

    2012-01-01

    The ASEAN+3 Bond Market Guide contains the comprehensive reports of the ASEAN+3 Bond Market Forum Sub-Forum 1 (SF1) and Sub-Forum 2 (SF2). The SF1 report (Volume 1) analyzes the harmonization and standardization of the existing bond markets in the ASEAN+3. It also contains the individual market guides of 11 economies under the ASEAN+3 Bond Market Forum (ABMF). The SF2 report (Volume 2) provides an overview of the ASEAN+3 bond markets and their infrastructures, as well as issues confronted by ...

  12. 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...

  13. Hydrogen bonding in ionic liquids.

    Science.gov (United States)

    Hunt, Patricia A; Ashworth, Claire R; Matthews, Richard P

    2015-03-01

    Ionic liquids (IL) and hydrogen bonding (H-bonding) are two diverse fields for which there is a developing recognition of significant overlap. Doubly ionic H-bonds occur when a H-bond forms between a cation and anion, and are a key feature of ILs. Doubly ionic H-bonds represent a wide area of H-bonding which has yet to be fully recognised, characterised or explored. H-bonds in ILs (both protic and aprotic) are bifurcated and chelating, and unlike many molecular liquids a significant variety of distinct H-bonds are formed between different types and numbers of donor and acceptor sites within a given IL. Traditional more neutral H-bonds can also be formed in functionalised ILs, adding a further level of complexity. Ab initio computed parameters; association energies, partial charges, density descriptors as encompassed by the QTAIM methodology (ρBCP), qualitative molecular orbital theory and NBO analysis provide established and robust mechanisms for understanding and interpreting traditional neutral and ionic H-bonds. In this review the applicability and extension of these parameters to describe and quantify the doubly ionic H-bond has been explored. Estimating the H-bonding energy is difficult because at a fundamental level the H-bond and ionic interaction are coupled. The NBO and QTAIM methodologies, unlike the total energy, are local descriptors and therefore can be used to directly compare neutral, ionic and doubly ionic H-bonds. The charged nature of the ions influences the ionic characteristics of the H-bond and vice versa, in addition the close association of the ions leads to enhanced orbital overlap and covalent contributions. The charge on the ions raises the energy of the Ylp and lowers the energy of the X-H σ* NBOs resulting in greater charge transfer, strengthening the H-bond. Using this range of parameters and comparing doubly ionic H-bonds to more traditional neutral and ionic H-bonds it is clear that doubly ionic H-bonds cover the full range of weak

  14. BWR plant-to-fleet water chemistry trends -- Past and present

    International Nuclear Information System (INIS)

    Good water chemistry control is important for the integrity and satisfactory performance of BWRs. A historical review of selected chemistry performance indicators (e.g., conductivity) illustrates the improved chemistry control today relative to that in the past as well as the ability to evaluate these operational indicators

  15. Additional disulfide bonds in insulin

    DEFF Research Database (Denmark)

    Vinther, Tine N; Pettersson, Ingrid; Huus, Kasper;

    2015-01-01

    The structure of insulin, a glucose homeostasis-controlling hormone, is highly conserved in all vertebrates and stabilized by three disulfide bonds. Recently, we designed a novel insulin analogue containing a fourth disulfide bond located between positions A10-B4. The N-terminus of insulin's B......-chain is flexible and can adapt multiple conformations. We examined how well disulfide bond predictions algorithms could identify disulfide bonds in this region of insulin. In order to identify stable insulin analogues with additional disulfide bonds, which could be expressed, the Cβ cut-off distance had...... in comparison to analogues with additional disulfide bonds that were more difficult to predict. In contrast, addition of the fourth disulfide bond rendered all analogues resistant to fibrillation under stress conditions and all stable analogues bound to the insulin receptor with picomolar affinities. Thus...

  16. Modeling the surface chemistry of biomass model compounds on oxygen-covered Rh(100).

    Science.gov (United States)

    Caglar, B; Niemantsverdriet, J W Hans; Weststrate, C J Kees-Jan

    2016-08-24

    Rhodium-based catalysts are potential candidates to process biomass and serve as a representation of the class of noble metal catalysts for biomass-related processes. Biomass can be processed in aqueous media (hydrolysis and aqueous phase reforming), and in this case the surface chemistry involves hydroxyl (OH) species. In our study this was modelled by the presence of pre-adsorbed oxygen. Ethylene glycol, with a hydroxyl group on every carbon atom, serves as a model compound to understand the conversion of biomass derived molecules into desirable chemicals on catalytically active metal surfaces. Ethanol (containing one OH group) serves as a reference molecule for ethylene glycol (containing two OH groups) to understand the interaction of C-OH functionalities with a Rh(100) surface. The surface chemistry of ethylene glycol and ethanol in the presence of pre-adsorbed oxygen on a Rh(100) surface has been studied via temperature programmed reaction spectroscopy (TPRS) and reflection absorption infrared spectroscopy (RAIRS) using various coverages of O(ad) and ethylene glycol and ethanol. Pre-adsorbed oxygen alters the decomposition chemistry of both compounds, thereby affecting the product distribution. Under an oxygen-lean condition, the selectivity to produce methane from ethanol is enhanced significantly (4.5-fold with respect to that obtained on the oxygen-free surface). For ethylene glycol, oxygen-lean conditions promote the formation of formaldehyde, with 10-15% selectivity. In addition, with Oad present the fraction of molecules that decompose on the surface increases 2-fold for ethanol and 1.5-fold for ethylene glycol, due to fast O-H bond activation by pre-adsorbed oxygen. Under oxygen-rich conditions, the decomposition products are mainly oxidized to carbon dioxide and water for both molecules. In this condition, the promotion effect provided by adsorbed oxygen for the dissociative adsorption of ethanol and ethylene glycol is reduced due to the site blocking

  17. Experimental quantification of electrostatics in X-H···π hydrogen bonds

    OpenAIRE

    Saggu, Miguel; Levinson, Nicholas M.; Boxer, Steven G.

    2012-01-01

    Hydrogen bonds are ubiquitous in chemistry and biology. The physical forces that govern hydrogen bonding interactions have been heavily debated, with much of the discussion focused on the relative contributions of electrostatic vs. quantum mechanical effects. In principle, the vibrational Stark effect (VSE), the response of a vibrational mode to electric field, can provide an experimental method for parsing such interactions into their electrostatic and non-electrostatic components. In a prev...

  18. Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

    Science.gov (United States)

    2013-01-01

    Summary Organophosphorus compounds are important in organic chemistry. This review article covers emerging, powerful synthetic approaches to organophosphorus compounds by homolytic substitution at phosphorus with a carbon-centered radical. Phosphination reagents include diphosphines, chalcogenophosphines and stannylphosphines, which bear a weak P–heteroatom bond for homolysis. This article deals with two transformations, radical phosphination by addition across unsaturated C–C bonds and substitution of organic halides. PMID:23843922

  19. Political Culture and Covalent Bonding: A Conceptual Model of Political Culture Change

    OpenAIRE

    Camelia Florela Voinea

    2015-01-01

    Our class of models aims at explaining the dynamics of political attitude change by means of the dynamic changes in values, beliefs, norms and knowledge with which it is associated. The model constructs a political culture perspective over the relationship between macro and micro levels of a society and polity. The model defines the bonding mechanism as a basic mechanism of the political culture change by taking inspiration from the valence bonding theory in Chemistry, which has inspired the ...

  20. Chemistry at large

    Directory of Open Access Journals (Sweden)

    Jeremy. K.M. Sanders

    2007-06-01

    Full Text Available A new book introduces young researchers to supramolecular chemistry, starting from the basics and working up to the more complicated aspects of the topic. While the text is inspiring for new graduates, it lacks a critical view.