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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. Dynamic Covalent Chemistry within Biphenyl Scaffolds: Reversible Covalent Bonding, Control of Selectivity, and Chirality Sensing with a Single System.

    Science.gov (United States)

    Ni, Cailing; Zha, Daijun; Ye, Hebo; Hai, Yu; Zhou, Yuntao; Anslyn, Eric V; You, Lei

    2018-01-26

    Axial chirality is a prevalent and important phenomenon in chemistry. Herein we report a combination of dynamic covalent chemistry and axial chirality for the development of a versatile platform for the binding and chirality sensing of multiple classes of mononucleophiles. An equilibrium between an open aldehyde and its cyclic hemiaminal within biphenyl derivatives enabled the dynamic incorporation of a broad range of alcohols, thiols, primary amines, and secondary amines with high efficiency. Selectivity toward different classes of nucleophiles was also achieved by regulating the distinct reactivity of the system with external stimuli. Through induced helicity as a result of central-to-axial chirality transfer, the handedness and ee values of chiral monoalcohol and monoamine analytes were reported by circular dichroism. The strategies introduced herein should find application in many contexts, including assembly, sensing, and labeling. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. The chemical bond in inorganic chemistry the bond valence model

    CERN Document Server

    Brown, I David

    2016-01-01

    The bond valence model is a version of the ionic model in which the chemical constraints are expressed in terms of localized chemical bonds formed by the valence charge of the atoms. Theorems derived from the properties of the electrostatic flux predict the rules obeyed by both ionic and covalent bonds. They make quantitative predictions of coordination number, crystal structure, bond lengths and bond angles. Bond stability depends on the matching of the bonding strengths of the atoms, while the conflicting requirements of chemistry and space lead to the structural instabilities responsible for the unusual physical properties displayed by some materials. The model has applications in many fields ranging from mineralogy to molecular biology.

  4. 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...

  5. 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.

  6. Hydrogen Bond Basicity Prediction for Medicinal Chemistry Design.

    Science.gov (United States)

    Kenny, Peter W; Montanari, Carlos A; Prokopczyk, Igor M; Ribeiro, Jean F R; Sartori, Geraldo Rodrigues

    2016-05-12

    Hydrogen bonding is discussed in the context of medicinal chemistry design. Minimized molecular electrostatic potential (Vmin) is shown to be an effective predictor of hydrogen bond basicity (pKBHX), and predictive models are presented for a number of hydrogen bond acceptor types relevant to medicinal chemistry. The problems posed by the presence of nonequivalent hydrogen bond acceptor sites in molecular structures are addressed by using nonlinear regression to fit measured pKBHX to calculated Vmin. Predictions are made for hydrogen bond basicity of fluorine in situations where relevant experimental measurements are not available. It is shown how predicted pKBHX can be used to provide insight into the nature of bioisosterism and to profile heterocycles. Examples of pKBHX prediction for molecular structures with multiple, nonequivalent hydrogen bond acceptors are presented.

  7. How Do Organic Chemistry Students Understand and Apply Hydrogen Bonding?

    Science.gov (United States)

    Henderleiter, J.; Smart, R.; Anderson, J.; Elian, O.

    2001-08-01

    Students completing a year-long organic chemistry sequence were interviewed to assess how they understood, explained, and applied knowledge of hydrogen bonding to the physical behavior of molecules. Students were asked to define hydrogen bonding and explain situations in which hydrogen bonding could occur. They were asked to predict and explain how hydrogen bonding influences boiling point, the solubility of molecules, and NMR and IR spectra. Results suggest that although students may be able to give appropriate definitions of hydrogen bonding and may recognize when this phenomenon can occur, significant numbers cannot apply their knowledge of hydrogen bonding to physical properties of molecules or to the interpretation of spectral data. Some possess misconceptions concerning boiling points and the ability of molecules to induce hydrogen bonding. Instructional strategies must be adjusted to address these issues.

  8. 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.

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

    OpenAIRE

    Özge Özyalçın Oskay, Sinem Dinçol

    2011-01-01

    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 gr...

  10. Selecting automation for the clinical chemistry laboratory.

    Science.gov (United States)

    Melanson, Stacy E F; Lindeman, Neal I; Jarolim, Petr

    2007-07-01

    Laboratory automation proposes to improve the quality and efficiency of laboratory operations, and may provide a solution to the quality demands and staff shortages faced by today's clinical laboratories. Several vendors offer automation systems in the United States, with both subtle and obvious differences. Arriving at a decision to automate, and the ensuing evaluation of available products, can be time-consuming and challenging. Although considerable discussion concerning the decision to automate has been published, relatively little attention has been paid to the process of evaluating and selecting automation systems. To outline a process for evaluating and selecting automation systems as a reference for laboratories contemplating laboratory automation. Our Clinical Chemistry Laboratory staff recently evaluated all major laboratory automation systems in the United States, with their respective chemistry and immunochemistry analyzers. Our experience is described and organized according to the selection process, the important considerations in clinical chemistry automation, decisions and implementation, and we give conclusions pertaining to this experience. Including the formation of a committee, workflow analysis, submitting a request for proposal, site visits, and making a final decision, the process of selecting chemistry automation took approximately 14 months. We outline important considerations in automation design, preanalytical processing, analyzer selection, postanalytical storage, and data management. Selecting clinical chemistry laboratory automation is a complex, time-consuming process. Laboratories considering laboratory automation may benefit from the concise overview and narrative and tabular suggestions provided.

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

    Science.gov (United States)

    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, RAC...

  12. Feasibility of Integration of Selected Aspects of (CBA) Chemistry, (CHEMS) Chemistry and (PSSC) Physics into a Two Year Physical Science Sequence.

    Science.gov (United States)

    Fiasca, Michael Aldo

    Compared, for selected outcomes, were integrated chemistry-physics courses with chemistry and physics courses taught separately. Three classes studying integrated Physical Science Study Committee (PSSC)-Chemical Bond Approach (CBA), and three classes studying integrated Physical Science Study Committee-Chemical Education Materials Study (CHEMS)…

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

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2013-01-01

    -scale DFT studies of inorganic systems in catalysis and bioinorganic chemistry rely directly on the ability to balance correlation effects in the involved bonds across the s-, p-, and d-blocks. This review concerns recent efforts to describe such bonds accurately and consistently across the s-, p-, and d......-blocks. Physical effects and ingredients in functionals, their systematic errors, and approaches to deal with them are discussed, in order to identify broadly applicable methods for inorganic chemistry....

  14. Bond-selective control of a gas-surface reaction

    Science.gov (United States)

    Killelea, Daniel R.

    The prospect of using light to selectively control chemical reactions has tantalized chemists since the development of the laser. Unfortunately, the realization of laser-directed chemistry is frequently thwarted by the randomization of energy within the molecule through intramolecular vibrational energy distribution (IVR). However, recent results showing vibrational mode-specific reactivity on metal surfaces suggest that IVR may not always be complete for gas-surface reactions. Here, we combine molecular beam techniques and direct laser excitation to characterize the bond-specific reactivity of trideuteromethane on a Ni(111) surface. Our results reveal important details about how vibrational energy is distributed in the reactive molecule. We use a molecular beam to direct state-selected trideuteromethane (CHD 3) molecules onto a nickel single crystal sample and use the results we obtain to describe the flow of vibrational energy in the methane-surface reaction complex. We show that CHD3 molecules initially excited to v=1, J=2, K=0 of the v 1 symmetric C-H stretching mode will dissociate exclusively via C-H cleavage on Ni(111). This result highlights the localization of vibrational energy in the reaction complex, despite the presence of many energy exchange channels with the high state-density surface. We demonstrate, for the first time, highly parallel bond-selective control of a heterogeneously catalyzed reaction. We place our results in the context of recent experiments investigating IVR for molecules in both the gas phase and liquid solutions. If IVR is fast on the reaction timescale, vibrational energy would be randomly distributed throughout the nascent methane-surface reaction complex and vibrational mode-specific behavior would not occur. The short timescale of a direct gas-surface collision may explain how the exchange of energy via IVR is limited to only a small subset of the energetic configurations available to the reaction complex. This framework

  15. Role of the H bond network in the radiation chemistry of hydrated systems

    International Nuclear Information System (INIS)

    Pommeret, S.; Renault, J.P.; Caeer, S.Le; Vigneron, G.; Vuilleumier, R.; Bratos, S.; Leicknam, J.Cl.

    2006-01-01

    In the present contribution a review of the recent work on the H bond dynamics, in absence of any reactant and a new theory that unambiguously establishes a new link between spectroscopic observation and geometric properties is presented, along with results on the radiation chemistry of nanoporous media and its influence on the H bond network of an interface

  16. 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

  17. Covalent-Bond Formation via On-Surface Chemistry.

    Science.gov (United States)

    Held, Philipp Alexander; Fuchs, Harald; Studer, Armido

    2017-05-02

    In this Review article pioneering work and recent achievements in the emerging research area of on-surface chemistry is discussed. On-surface chemistry, sometimes also called two-dimensional chemistry, shows great potential for bottom-up preparation of defined nanostructures. In contrast to traditional organic synthesis, where reactions are generally conducted in well-defined reaction flasks in solution, on-surface chemistry is performed in the cavity of a scanning probe microscope on a metal crystal under ultrahigh vacuum conditions. The metal first acts as a platform for self-assembly of the organic building blocks and in many cases it also acts as a catalyst for the given chemical transformation. Products and hence success of the reaction are directly analyzed by scanning probe microscopy. This Review provides a general overview of this chemistry highlighting advantages and disadvantages as compared to traditional reaction setups. The second part of the Review then focuses on reactions that have been successfully conducted as on-surface processes. On-surface Ullmann and Glaser couplings are addressed. In addition, cyclodehydrogenation reactions and cycloadditions are discussed and reactions involving the carbonyl functionality are highlighted. Finally, the first examples of sequential on-surface chemistry are considered in which two different functionalities are chemoselectively addressed. The Review gives an overview for experts working in the area but also offers a starting point to non-experts to enter into this exciting new interdisciplinary research field. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Towards 'selection rules' in the radiation chemistry of molecular materials

    International Nuclear Information System (INIS)

    Feldman, V.I.; Inst. of Synthetic Polymetric Materials, Moscow; Moscow State Univ.

    2002-01-01

    Complete text of publication follows. There are a lot of experimental evidences suggesting that the primary radiation-induced events in organic solids and polymers are highly selective and sensitive to conformation, molecular packing, matrix environment, etc. Nevertheless, specific 'selection rules' in the radiation chemistry of molecules in solids are still not established. This contribution presents a review of our recent studies of the radiation damage in organic molecules in low-temperature matrices and polymers aimed at elucidation of basic physical factors controlling selectivity of the primary chemical events. The following aspects will be analyzed: 1. 'Fine tuning' effects in positive hole trapping in rigid systems containing molecular 'traps' with close ionization energy. 2. Selective chemical bond weakening in ionized molecules: experimental and theoretical results. 3. Matrix-assisted and matrix-controlled chemical reactions of ionized molecules in solid media (including the effect of 'matrix-catalysis'). 4. Effect of excess energy on the fate of ionized molecules in solid matrices: the role of intramolecular and intermolecular relaxation. Finally, the problem of experimental and theoretical simulation of the distribution of the radiation-induced events in complex molecular systems and polymers will be addressed

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

    NARCIS (Netherlands)

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

    2017-01-01

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

  20. 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...... consider an ozone molecule with isotopic substitution, that is, (OOO)-O-16-O-16-O-18. It is shown that asymmetric bond stretching can be created in simple (intense) laser fields. We predict that an alternating high selectivity between the channels O-16+(OO)-O-16-O-18 and (OO)-O-16-O-16+ O-18 can...

  1. Structure, Bonding and Surface Chemistry of Metal Oxide Nanoclusters

    Science.gov (United States)

    2015-06-23

    an electrospray ionization time-of-flight (ESI-TOF) mass spectrometer to the lab (PerSeptive Biosystems Mariner), which provides a different...with this Project Faculty: Professor Michael A. Duncan (one month summer salary) Prof. Heather Abbott -Lyons, summer visiting faculty and...Distribution approved for public release. 4. H. L. Abbott , A. D. Brathwaite and M. A. Duncan, "Infrared spectroscopy and structures of mass-selected

  2. 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...

  3. Optimal control of bond selectivity in unimolecular reactions

    International Nuclear Information System (INIS)

    Shi Shenghua; Rabitz, H.

    1991-01-01

    The optimal control theory approach to designing optimal fields for bond-selective unimolecular reactions is presented. A set of equations for determining the optimal fields, which will lead to the achievement of the objective of bond-selective dissociation is developed. The numerical procedure given for solving these equations requires the repeated calculation of the time propagator for the system with the time-dependent Hamiltonian. The splitting approximation combined with the fast Fourier transform algorithm is used for computing the short time propagator. As an illustrative example, a model linear triatomic molecule is treated. The model system consists of two Morse oscillators coupled via kinetic coupling. The magnitude of the dipoles of the two Morse oscillators are the same, the fundamental frequencies are almost the same, but the dissociation energies are different. The rather demanding objective under these conditions is to break the stronger bond while leaving the weaker one intact. It is encouraging that the present computational method efficiently gives rise to the optimal field, which leads to the excellent achievement of the objective of bond selective dissociation. (orig.)

  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 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. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. 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.

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

    Science.gov (United States)

    Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

    2015-04-01

    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.

  8. Experimental Realisation of Elusive Multiple-bonded Aluminium Compounds: A New Horizon in the Aluminium Chemistry.

    Science.gov (United States)

    Inoue, Shigeyoshi; Bag, Prasenjit; Weetman, Catherine

    2018-05-23

    Synthesis and isolation of stable main group compounds featuring multiple bonds has been of keen interest for the last several decades. Multiply bonded complexes were obtained using sterically demanding substituents that provide kinetic and thermodynamic stability. Many of these compounds have unusual structural and electronic properties that challenges the classical concept of covalent multiple bonding. In contrast, analogous aluminium compounds are scarce in spite of its high natural abundance. The parent dialumene (Al2H2) has been calculated to be extremely weak, thus making Al multiple bonds a challenging synthetic target. This review provides an overview of these recent advances in the cutting edge synthetic approaches used to obtain aluminium homo- and heterodiatomic multiply bonded complexes. Additionally, the reactivity of these novel compounds towards various small molecules and reagents will be discussed herein. This review provides an overview on the current progress in aluminium multiple bond chemistry and the careful ligand design required to stabilise these reactive species. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

    KAUST Repository

    Samantaray, Manoja

    2015-08-18

    In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C–H and C–C bonds of paraffin is a long-standing challenge because of intrinsic low reactivity. There are many concepts derived from surface organometallic chemistry (SOMC): surface organometallic fragments are always intermediates in heterogeneous catalysis. The study of their synthesis and reactivity is a way to rationalize mechanism of heterogeneous catalysis and to achieve structure activity relationship. By surface organometallic chemistry one can enter any catalytic center by a reaction intermediate leading in fine to single site catalysts. With surface organometallic chemistry one can coordinate to the metal which can play a role in different elementary steps leading for example to C–H activation and Olefin metathesis. Because of the development of SOMC there is a lot of space for the improvement of homogeneous catalysis. After the 1997 discovery of alkane metathesis using silica-supported tantalum hydride by Basset et al. at low temperature (150ºC) the focus in this area was shifted to the discovery of more and more challenging surface complexes active in the application of C–H and C–C bond activation. Here we describe the evolution of well-defined metathesis catalyst with time as well as the effect of support on catalysis. We also describe here which metal–ligand combinations are responsible for a variety of C–H and C–C bond activation.

  10. Introducing Dynamic Combinatorial Chemistry: Probing the Substrate Selectivity of Acetylcholinesterase

    Science.gov (United States)

    Angelin, Marcus; Larsson, Rikard; Vongvilai, Pornrapee; Ramstrom, Olof

    2010-01-01

    In this laboratory experiment, college students are introduced to dynamic combinatorial chemistry (DCC) and apply it to determine the substrate selectivity of acetylcholinesterase (AChE). Initially, the students construct a chemical library of dynamically interchanging thioesters and thiols. Then, AChE is added and allowed to select and hydrolyze…

  11. 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.

  12. Surface chemistry and bonding configuration of ultrananocrystalline diamond surfaces and their effects on nanotribological properties

    International Nuclear Information System (INIS)

    Sumant, A. V.; Grierson, D. S.; Carpick, R. W.; Gerbi, J. E.; Carlisle, J. A.; Auciello, O.

    2007-01-01

    We present a comprehensive study of surface composition and nanotribology for ultrananocrystalline diamond (UNCD) surfaces, including the influence of film nucleation on these properties. We describe a methodology to characterize the underside of the films as revealed by sacrificial etching of the underlying substrate. This enables the study of the morphology and composition resulting from the nucleation and initial growth of the films, as well as the characterization of nanotribological properties which are relevant for applications including micro-/nanoelectromechanical systems. We study the surface chemistry, bonding configuration, and nanotribological properties of both the topside and the underside of the film with synchrotron-based x-ray absorption near-edge structure spectroscopy to identify the bonding state of the carbon atoms, x-ray photoelectron spectroscopy to determine the surface chemical composition, Auger electron spectroscopy to further verify the composition and bonding configuration, and quantitative atomic force microscopy to study the nanoscale topography and nanotribological properties. The films were grown on SiO 2 after mechanically polishing the surface with detonation synthesized nanodiamond powder, followed by ultrasonication in a methanol solution containing additional nanodiamond powder. The sp 2 fraction, morphology, and chemistry of the as-etched underside are distinct from the topside, exhibiting a higher sp 2 fraction, some oxidized carbon, and a smoother morphology. The nanoscale single-asperity work of adhesion between a diamond nanotip and the as-etched UNCD underside is far lower than for a silicon-silicon interface (59.2±2 vs 826±186 mJ/m 2 , respectively). Exposure to atomic hydrogen dramatically reduces nanoscale adhesion to 10.2±0.4 mJ/m 2 , at the level of van der Waals' interactions and consistent with recent ab initio calculations. Friction is substantially reduced as well, demonstrating a direct link between the

  13. Hydrogels Based on Dynamic Covalent and Non Covalent Bonds: A Chemistry Perspective

    Directory of Open Access Journals (Sweden)

    Francesco Picchioni

    2018-03-01

    Full Text Available Hydrogels based on reversible covalent bonds represent an attractive topic for research at both academic and industrial level. While the concept of reversible covalent bonds dates back a few decades, novel developments continue to appear in the general research area of gels and especially hydrogels. The reversible character of the bonds, when translated at the general level of the polymeric network, allows reversible interaction with substrates as well as responsiveness to variety of external stimuli (e.g., self-healing. These represent crucial characteristics in applications such as drug delivery and, more generally, in the biomedical world. Furthermore, the several possible choices that can be made in terms of reversible interactions generate an almost endless number of possibilities in terms of final product structure and properties. In the present work, we aim at reviewing the latest developments in this field (i.e., the last five years by focusing on the chemistry of the systems at hand. As such, this should allow molecular designers to develop a toolbox for the synthesis of new systems with tailored properties for a given application.

  14. Role of the H bond network in the radiation chemistry of hydrated systems

    International Nuclear Information System (INIS)

    Pommeret, S.; Renault, J.P.; Le Caer, S.; Vigneron, G.; Palmer, J.; Lima, M.; Righini, R.

    2006-01-01

    Introduction: In the present contribution, we want to address the influence of the H bond network on the observed reactivity of hydrated system. In radiation chemistry the primary species appear extremely simple and at the same time are very reactive. The comprehension of their dynamics is rather difficult since their reactivity involves the solvent molecules as reactant. Some of those species like the hydrated electron and the proton are highly hydrophilic, while others like the hydroxide radical and the H atom are rather hydrophobic. Both the hydrated electron and the H atom locate near a defect of the H bond network i.e. a cavity. As an example of the role of the environment in radical chemistry, when studying the radiation chemistry of porous media we noticed that the interface play a crucial role in the outcome of that chemistry. More particularly we observed that the silanol band of the silica/water interface was strongly affected by the irradiation even so no energy is directly absorbed by an interface. In this contribution, we will first review the recent work on the H bond dynamics, in absence of any reactant. We will then present recent results on the radiation chemistry of nanoporous media and its influence on the H bond network of an interface and will also present recent results obtained on the H bond dynamics at an alumina-water interface. All those results will be discussed in light of the H bonded nature of neat water. Radiation chemistry of an H bonded interface: A Fourier transformed infrared detection associated to an electron accelerator was developed so as to characterise in situ the effects of irradiation on various systems. The FT-IR spectrometer and the detector were moved out of the accelerator room to be protected against radiation. The infrared beam was guided on a distance of 6 meters by optical conduits and mirrors. The spectra were obtained from 100 scans accumulated with a Bruker Vertex 70 equipment operating with a 4 cm -1 resolution

  15. 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.

  16. Friedel-Crafts reaction of benzyl fluorides: selective activation of C-F bonds as enabled by hydrogen bonding.

    Science.gov (United States)

    Champagne, Pier Alexandre; Benhassine, Yasmine; Desroches, Justine; Paquin, Jean-François

    2014-12-08

    A Friedel-Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1-diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C-F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C-F bonds in the presence of other benzylic leaving groups. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Glutamic Acid Selective Chemical Cleavage of Peptide Bonds.

    Science.gov (United States)

    Nalbone, Joseph M; Lahankar, Neelam; Buissereth, Lyssa; Raj, Monika

    2016-03-04

    Site-specific hydrolysis of peptide bonds at glutamic acid under neutral aqueous conditions is reported. The method relies on the activation of the backbone amide chain at glutamic acid by the formation of a pyroglutamyl (pGlu) imide moiety. This activation increases the susceptibility of a peptide bond toward hydrolysis. The method is highly specific and demonstrates broad substrate scope including cleavage of various bioactive peptides with unnatural amino acid residues, which are unsuitable substrates for enzymatic hydrolysis.

  18. Understanding Boron through Size-Selected Clusters: Structure, Chemical Bonding, and Fluxionality

    Energy Technology Data Exchange (ETDEWEB)

    Sergeeva, Alina P.; Popov, Ivan A.; Piazza, Zachary A.; Li, Wei-Li; Romanescu, Constantin; Wang, Lai S.; Boldyrev, Alexander I.

    2014-04-15

    /C analogy. It is believed that the electronic transmutation concept will be effective and valuable in aiding the design of new boride materials with predictable properties. The study of boron clusters with intermediate properties between those of individual atoms and bulk solids has given rise to a unique opportunity to broaden the frontier of boron chemistry. Understanding boron clusters has spurred experimentalists and theoreticians to find new boron-based nanomaterials, such as boron fullerenes, nanotubes, two-dimensional boron, and new compounds containing boron clusters as building blocks. Here, a brief and timely overview is presented addressing the recent progress made on boron clusters and the approaches used in the authors’ laboratories to determine the structure, stability, and chemical bonding of size-selected boron clusters by joint photoelectron spectroscopy and theoretical studies. Specifically, key findings on all-boron hydrocarbon analogues, metal-centered boron wheels, and electronic transmutation in boron clusters are summarized.

  19. Selection criteria for the best secondary water chemistry

    International Nuclear Information System (INIS)

    Nordmann, F.; Fiquet, J.M.

    1996-01-01

    This paper describes, for PWR plants, the approach for selecting the best chemistry-pH, amine, corrosion inhibitors-according to the secondary system characteristics, such as presence or not of copper alloys, steam generator tubing alloy, tube support plate design, sludge pile importance. The impact of condensate polisher, sludge lancing, chemical cleaning, as well as other ways of eliminating undesirable compounds or mitigating them are also discussed. For plants with simultaneous presence of carbon steel and copper alloys, alternate amines like morpholine, or new reagents such as ethanolamine (ETA), can be selected to manage erosion-corrosion of carbon steel and decrease corrosion transport, at a pH acceptable for copper alloys (9.2 at 25 C). In more recent units, with an all ferrous system, a high pH operation, with only hydrazine addition, the easiest way, or with combined hydrazine and morpholine or ETA will be of some benefit against steam generator corrosion. When Alloy 600 has been selected, inhibitors such as boric acid, or maybe titanium oxide or cerium in the future, needs to be added in steam generators in order to decrease intergranular corrosion progression. In addition, caustic and lead contaminations must be strictly avoided, while sludge and deposits will be eliminated by lancing and chemical cleaning, if necessary. (orig.)

  20. 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…

  1. A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds.

    Science.gov (United States)

    Scamp, Ryan J; Jirak, James G; Dolan, Nicholas S; Guzei, Ilia A; Schomaker, Jennifer M

    2016-06-17

    The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon-hydrogen (C-H) bond amination of activated secondary C-H bonds over tertiary alkyl C(sp(3))-H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C-H bonds over tertiary alkyl C(sp(3))-H bonds.

  2. [Bond strengths of customized titanium brackets manufactured by selective laser melting].

    Science.gov (United States)

    Zou, Dao-xing; Wang, Ze-min; Guo, Hong-ming; Li, Song; Bai, Yu-xing

    2013-07-01

    To investigate the bond strengths of customized titanium bracket manufactured by selective laser melting. Eighty human premolars which had been extracted for orthodontic purpose were collected and divided randomly (by random table) into two groups (customized bracket group and 3M bracket group, 40 molars in each group). The 35% phosphoric acid was used for etching and the brackets were bonded with 3M Unitek bonding adhesive. All bonded specimens were placed in saline for 24 hours at room temperature and were tested on DWD3050 electronic testing machine to determine the shear bond strength and tensile bond strength. After debonding, the adhesive remnant indexes (ARI) were recorded. The shear bond strengths of customized brackets was 6.80 (6.20, 8.32) MPa, which was significantly lower than that of the 3M brackets [10.46 (9.72, 11.48) MPa] (Z = -3.463, P < 0.05). And the tensile bond strengths of customized brackets was (6.93 ± 1.21) MPa, which was significantly higher than that of the 3M brackets [(5.88 ± 1.23) MPa] (t = 2.81, P < 0.05). No significant difference was found in the ARI between two different kinds of the brackets. The shear bond strength and tensile bond strength of both kinds of brackets were enough for clinic application.

  3. Selective C(sp2)-C(sp) bond cleavage: the nitrogenation of alkynes to amides.

    Science.gov (United States)

    Qin, Chong; Feng, Peng; Ou, Yang; Shen, Tao; Wang, Teng; Jiao, Ning

    2013-07-22

    Breakthrough: A novel catalyzed direct highly selective C(sp2)-C(sp) bond functionalization of alkynes to amides has been developed. Nitrogenation is achieved by the highly selective C(sp2)-C(sp) bond cleavage of aryl-substituted alkynes. The oxidant-free and mild conditions and wide substrate scope make this method very practical. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. 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…

  5. 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

    2016-01-01

    Abstract 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 1H NMR anion binding results. PMID:27436297

  6. Information resources and material selection in bonded restorations among Korean dentists.

    Science.gov (United States)

    Chang, Juhea; Kim, Hae-Young; Cho, Byeong Hoon; Lee, In Bog; Son, Ho Hyun

    2009-12-01

    To elucidate how dentists access knowledge sources when choosing adhesive agents for bonded restoration and whether these resources influenced the selection of materials. A national survey was carried out involving dentists in South Korea. The questionnaire included the status of the operator, clinical techniques, and materials. A total of 12,193 e-mails were distributed, 2632 were opened by recipients, and 840 responses were collected. For primary information resources in material selection, 55.8% (n = 469) of the responders mentioned continuing education. This selection criteria varied according to the working status of the clinician (p choice of bonding system was influenced by of the length of the career (p < 0.0001), and the preferred bonding systems differed according to the source of the information (p = 0.035). The popular bonding systems were not ranked according to the bonding strategy, but a preference was found for specific brands or manufacturers. To decrease the confusion of clinicians related to the selection of bonding materials, evidence-based guidelines need to be comprehensibly organized and efficiently approached in clinics.

  7. Bond selective photochemistry in CH2BrI through electronic excitation at 210 nm

    International Nuclear Information System (INIS)

    Butler, L.J.; Hintsa, E.J.; Lee, Y.T.

    1986-01-01

    To explore the possibility of bond selective photochemistry in an excited electronic state, we have studied the photolysis of CH 2 BrI in a molecular beam at 210 nm. Following the direct local excitation of a repulsive transition on the C--Br bond at 210 nm, the fragments were detected by time-of-flight mass spectrometry. The dominant channel was found to be C--Br fission (60%) releasing an average of 15 kcal/mol into translation with the remainder reacting to form CH 2 +IBr and CH 2 +I+Br. There was no evidence for the primary fission of the C--I bond, making this the first clear example of the selective cleavage of a stronger bond in a molecule over the weakest one

  8. The Cosmic-Chemical Bond: Chemistry from the Big Bang to Planet Formation

    Science.gov (United States)

    Williams, D. A.; Hartquist, T. W.

    2013-01-01

    Introducing astrochemistry to a wide audience, this book describes how molecules formed in chemical reactions occur in a range of environments in interstellar and circumstellar space, from shortly after the Big Bang up to the present epoch. Stressing that chemistry in these environments needs to be "driven", it helps identify these drivers and the various chemical networks that operate giving rise to signature molecules that enable the physics of the region to be better understood. The book emphasises, in a non-mathematical way, the chemistry of the Milky Way Galaxy and its planet-forming regions, describes how other galaxies may have rather different chemistries and shows how chemistry was important even in the Early Universe when most of the elements had yet to be formed. This book will appeal to anyone with a general interest in chemistry, from students to professional scientists working in interdisciplinary areas and non-scientists fascinated by the evolving and exciting story of chemistry in the cosmos.

  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. 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.

  11. 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…

  12. New Concept of C–H and C–C Bond Activation via Surface Organometallic Chemistry

    KAUST Repository

    Samantaray, Manoja; Dey, Raju; Kavitake, Santosh Giridhar; Basset, Jean-Marie

    2015-01-01

    In this chapter we describe the recent applications of well-defined oxidesupported metal alkyls/alkylidenes/alkylidynes and hydrides of group IV, V, and VI transition metals in the field of C–H and C–C bond activation. The activation of ubiquitous C

  13. 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.

  14. 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.

  15. 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

    2016-04-07

    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.

  16. Integrating medicinal chemistry, organic/combinatorial chemistry, and computational chemistry for the discovery of selective estrogen receptor modulators with Forecaster, a novel platform for drug discovery.

    Science.gov (United States)

    Therrien, Eric; Englebienne, Pablo; Arrowsmith, Andrew G; Mendoza-Sanchez, Rodrigo; Corbeil, Christopher R; Weill, Nathanael; Campagna-Slater, Valérie; Moitessier, Nicolas

    2012-01-23

    As part of a large medicinal chemistry program, we wish to develop novel selective estrogen receptor modulators (SERMs) as potential breast cancer treatments using a combination of experimental and computational approaches. However, one of the remaining difficulties nowadays is to fully integrate computational (i.e., virtual, theoretical) and medicinal (i.e., experimental, intuitive) chemistry to take advantage of the full potential of both. For this purpose, we have developed a Web-based platform, Forecaster, and a number of programs (e.g., Prepare, React, Select) with the aim of combining computational chemistry and medicinal chemistry expertise to facilitate drug discovery and development and more specifically to integrate synthesis into computer-aided drug design. In our quest for potent SERMs, this platform was used to build virtual combinatorial libraries, filter and extract a highly diverse library from the NCI database, and dock them to the estrogen receptor (ER), with all of these steps being fully automated by computational chemists for use by medicinal chemists. As a result, virtual screening of a diverse library seeded with active compounds followed by a search for analogs yielded an enrichment factor of 129, with 98% of the seeded active compounds recovered, while the screening of a designed virtual combinatorial library including known actives yielded an area under the receiver operating characteristic (AU-ROC) of 0.78. The lead optimization proved less successful, further demonstrating the challenge to simulate structure activity relationship studies.

  17. 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

  18. 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

  19. 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

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

    Czech Academy of Sciences Publication Activity Database

    Sato, H.; Dybal, Jiří; Murakami, R.; Noda, I.; Ozaki, Y.

    744-747, - (2005), s. 35-46 ISSN 0022-2860 R&D Projects: GA AV ČR IAA4050208 Keywords : infrared and Raman spectroscopy * quantum chemical calculation * C-H...O hydrogen bonding Subject RIV: CD - Macromolecular Chemistry Impact factor: 1.440, year: 2005

  1. 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

    2016-09-05

    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. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  2. Presidential Green Chemistry Challenge: 2007 Academic Award

    Science.gov (United States)

    Presidential Green Chemistry Challenge 2007 award winner, Professor Michael J. Krische, developed selective C-C bond-forming hydrogenation without organometallic reagents, eliminating hazardous reagents and hazardous waste.

  3. Organometallic complex chemistry of plutonium and selected lanthanides

    International Nuclear Information System (INIS)

    Seemann, U.

    1987-01-01

    This study deals with the metallo-organic chemistry of plutonium and also with that of some lanthanides. For plutonium, the conversion of Cs 2 PuCl 6 with four equivalents KCp is investigated. In the series Sm, Gd, Dy and Er, compounds of the type Cp 2 LnX and the base adducts with acetonitrile are analysed. The ligand X passes the series Cl, N 3 , NCS and NCO. Both, the thermal and the vibrational spectroscopic behaviour is investigated. In addition, the effect of a changed ligand sphere on the optical spectrum is discussed. The adduct-free compounds are described by a ternary reaction not yet known from literature. For the first time, force constant calculations are carried out on metallo-organic compounds of lanthanides. With the exception of Cp 2 LnCl compounds, all compouds are presented for the first time in the framework of this study. (orig.) [de

  4. Contributions to reversed-phase column selectivity: III. Column hydrogen-bond basicity.

    Science.gov (United States)

    Carr, P W; Dolan, J W; Dorsey, J G; Snyder, L R; Kirkland, J J

    2015-05-22

    Column selectivity in reversed-phase chromatography (RPC) can be described in terms of the hydrophobic-subtraction model, which recognizes five solute-column interactions that together determine solute retention and column selectivity: hydrophobic, steric, hydrogen bonding of an acceptor solute (i.e., a hydrogen-bond base) by a stationary-phase donor group (i.e., a silanol), hydrogen bonding of a donor solute (e.g., a carboxylic acid) by a stationary-phase acceptor group, and ionic. Of these five interactions, hydrogen bonding between donor solutes (acids) and stationary-phase acceptor groups is the least well understood; the present study aims at resolving this uncertainty, so far as possible. Previous work suggests that there are three distinct stationary-phase sites for hydrogen-bond interaction with carboxylic acids, which we will refer to as column basicity I, II, and III. All RPC columns exhibit a selective retention of carboxylic acids (column basicity I) in varying degree. This now appears to involve an interaction of the solute with a pair of vicinal silanols in the stationary phase. For some type-A columns, an additional basic site (column basicity II) is similar to that for column basicity I in primarily affecting the retention of carboxylic acids. The latter site appears to be associated with metal contamination of the silica. Finally, for embedded-polar-group (EPG) columns, the polar group can serve as a proton acceptor (column basicity III) for acids, phenols, and other donor solutes. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. Multireference theoretical investigation on selectivity of the bond fissions in photodissociation of acetyl cyanide

    Science.gov (United States)

    Xiao, Hong-Yan; Liu, Ya-Jun; Fang, Wei-Hai

    2007-12-01

    The selectivity of the C -CH3 and C-CN bond fissions upon excitation of acetyl cyanide at 193nm has been investigated at the theoretical level of multistate complete active space self-consistent field second order perturbation. The calculated results indicated that the initially excited S3 state relaxes to S2 via ultrafast internal conversion. The S2 state could dissociate via two pathways. One, adiabatically dissociates to CH3CO(X˜)+CN(Ã). The other one internally converts to S1 before S1 intersystem crossing to T1. The T1 state subsequently dissociates to two groups of products: CH3(X˜)+OCCN(X˜) and CH3CO(X˜)+CN(X˜). The experimentally observed preference branching of CN elimination over CH3 one and bond selectivity are the results of the competition between the adiabatic and nonadiabatic dynamics of the S2 state.

  6. Selective bond cleavage in potassium collisions with pyrimidine bases of DNA.

    Science.gov (United States)

    Almeida, Diogo; Ferreira da Silva, Filipe; García, Gustavo; Limão-Vieira, Paulo

    2013-01-11

    Electron transfer in alkali-molecule collisions to gas phase thymine and uracil yielding H- formation is selectively controlled in the energy range between 5.3 and 66.1 eV. By tuning the collision energy, electron transfer from the alkali to partly deuterated thymine, methylated thymine at the N1 and methylated uracil at the N3 positions, H- loss proceeds not only through the breaking of the (C-H) against (N-H) bonds but also through N1 against N3 sites. Such selectivity, as far as bond and site are concerned, is here reported for the first time by electron transfer induced dissociation experiments in alkali-molecule collisions.

  7. An effective hierarchical model for the biomolecular covalent bond: an approach integrating artificial chemistry and an actual terrestrial life system.

    Science.gov (United States)

    Oohashi, Tsutomu; Ueno, Osamu; Maekawa, Tadao; Kawai, Norie; Nishina, Emi; Honda, Manabu

    2009-01-01

    Under the AChem paradigm and the programmed self-decomposition (PSD) model, we propose a hierarchical model for the biomolecular covalent bond (HBCB model). This model assumes that terrestrial organisms arrange their biomolecules in a hierarchical structure according to the energy strength of their covalent bonds. It also assumes that they have evolutionarily selected the PSD mechanism of turning biological polymers (BPs) into biological monomers (BMs) as an efficient biomolecular recycling strategy We have examined the validity and effectiveness of the HBCB model by coordinating two complementary approaches: biological experiments using existent terrestrial life, and simulation experiments using an AChem system. Biological experiments have shown that terrestrial life possesses a PSD mechanism as an endergonic, genetically regulated process and that hydrolysis, which decomposes a BP into BMs, is one of the main processes of such a mechanism. In simulation experiments, we compared different virtual self-decomposition processes. The virtual species in which the self-decomposition process mainly involved covalent bond cleavage from a BP to BMs showed evolutionary superiority over other species in which the self-decomposition process involved cleavage from BP to classes lower than BM. These converging findings strongly support the existence of PSD and the validity and effectiveness of the HBCB model.

  8. Cycloheptatrienyl zirconium sandwich complexes with lewis basic phospholyl ligands (phosphatrozircenes): synthesis, structure, bonding and coordination chemistry.

    Science.gov (United States)

    Glöckner, Andreas; Bannenberg, Thomas; Büschel, Susanne; Daniliuc, Constantin G; Jones, Peter G; Tamm, Matthias

    2011-05-23

    The transmetalation reaction between [(η(7) -C(7) H(7) )ZrCl(tmeda)] (1; tmeda=N,N,N',N'-tetramethylethylenediamine) and various phospholide anions leads to a new class of mixed sandwich complexes: [(η(7)-C(7)H(7))Zr(η(5)-C(4)PMe(4))] (2), [(η(7)-C(7)H(7))Zr(η(5)-C(4)PH(2)Me(2))] (3) and [(η(7)-C(7)H(7))Zr(η(5)-C(4)PPhHMe(2))] (4). The presence of Lewis basic phosphorus atoms and Lewis acidic zirconium atoms allows ambiphilic behaviour to be observed, and X-ray diffraction analysis reveals dimeric arrangements for 2 and 3 with long intermolecular Zr-P bonds, whereas 4 remains monomeric in the solid state. DFT calculations indicate that the metal-phosphorus interaction is weak, and accordingly, complexes 2-4 act as monodentate ligands upon reaction with [W(CO)(5)(thf)]. The resulting complexes [W(CO)(5)(L)] 5-7 (L=2-4) were studied by IR spectroscopy and compared with the [W(CO)(5) ] complex 9, containing the phosphane-functionalised trozircene [(η(7)-C(7)H(7))Zr(η(5)-C(5)H(4)PPh(2))] (8). They all show a close resemblance to simple phosphanes, such as PMe(3) , although molecular orbital analysis of 2 reveals that the free electron pair in the phosphatrozircenes is not the HOMO. Four equivalents of 2 can replace 1,4-cyclooctadiene (COD) in [Ni(cod)(2)] to form the homoleptic, distorted tetrahedral complex [Ni{2}(4)] (10). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Bond strength of selected composite resin-cements to zirconium-oxide ceramic

    Science.gov (United States)

    Fons-Font, Antonio; Amigó-Borrás, Vicente; Granell-Ruiz, María; Busquets-Mataix, David; Panadero, Rubén A.; Solá-Ruiz, Maria F.

    2013-01-01

    Objectives: The aim of this study was to evaluate bond strengths of zirconium-oxide (zirconia) ceramic and a selection of different composite resin cements. Study Design: 130 Lava TM cylinders were fabricated. The cylinders were sandblasted with 80 µm aluminium oxide or silica coated with CoJet Sand. Silane, and bonding agent and/or Clearfil Ceramic Primer were applied. One hundred thirty composite cement cylinders, comprising two dual-polymerizing (Variolink II and Panavia F) and two autopolymerizing (Rely X and Multilink) resins were bonded to the ceramic samples. A shear test was conducted, followed by an optical microscopy study to identify the location and type of failure, an electron microscopy study (SEM and TEM) and statistical analysis using the Kruskal-Wallis test for more than two independent samples and Mann-Whitney for two independent samples. Given the large number of combinations, Bonferroni correction was applied (α=0.001). Results: Dual-polymerizing cements provided better adhesion values (11.7 MPa) than the autopolymerizing (7.47 MPa) (p-value M-Wzirconium-oxide ceramic, creating a more rough and retentive surface, thus providing an improved micromechanical interlocking between the cement and the ceramic. Key words:Shear bond strength, silica coating, surface treatment, zirconia ceramics, phosphate monomer. PMID:22926485

  10. Metal-ceramic bond strength of Co-Cr alloy fabricated by selective laser melting.

    Science.gov (United States)

    Xiang, Nan; Xin, Xian-Zhen; Chen, Jie; Wei, Bin

    2012-06-01

    This study was to evaluated the metal-ceramic bond strength of a Co-Cr dental alloy prepared using a selective laser melting (SLM) technique. Two groups comprised of twenty Co-Cr metal bars each were prepared using either a SLM or traditional lost-wax casting method. Ten bars from each group were moulded into standard ISO 9693:1999 dimensions of 25 mm × 3 mm × 0.5 mm with 1.1 mm of porcelain fused onto an 8 mm × 3 mm rectangular area in the centre of each bar. Metal-ceramic bonding was assessed using a three-point bending test. Fracture mode analysis and area fraction of adherence porcelain (AFAP) were determined by measuring Si content of specimens by SEM/EDS. Student's t-test within the groups demonstrated no significant difference for the mean bond strength between the SLM and traditional cast sample groups. While SEM/EDS analysis indicated a mixed fracture mode on the debonding interface of both the SLM and the cast groups, the SLM group showed significantly more porcelain adherence than the control group (p<0.05). The SLM metal-ceramic system exhibited a bonding strength that exceeds the requirement of ISO 9691:1999(E) and it even showed a better behaviour in porcelain adherence test comparable to traditional cast methods. Copyright © 2012 Elsevier Ltd. All rights reserved.

  11. Green chemistry: highly selective biocatalytic hydrolysis of nitrile compounds

    CSIR Research Space (South Africa)

    Brady, D

    2006-09-01

    Full Text Available ambient temperatures and moderate pH, thereby reducing environmental impact, minimising the cost of equipment and improving reaction safety2. A further benefit is that biocatalysts can synthesise complex chemicals selectively3. This avoids... nitrile group in a dinitrile molecule permits the incorporation of the unreacted nitrile into the final product or further functionalisation, such as reduction to an amino group. Hence, these enzymes can be used to provide access to specific complex...

  12. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    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 UF 3 and dissolved UF 4 , and, in some cases, between the dissolved uranium fluorides and graphite, and the UC 2 . Several aspects of coolant-salt chemistry are under investigation. Hydroxy and oxy compounds that could be formed in molten NaBF 4 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 U 4+ /U 3+ ratios in fuel salt was tested in a forced-convection loop over a six-month period. (LK)

  13. Tetrel Bonding as a Vehicle for Strong and Selective Anion Binding

    Directory of Open Access Journals (Sweden)

    Steve Scheiner

    2018-05-01

    Full Text Available Tetrel atoms T (T = Si, Ge, Sn, and Pb can engage in very strong noncovalent interactions with nucleophiles, which are commonly referred to as tetrel bonds. The ability of such bonds to bind various anions is assessed with a goal of designing an optimal receptor. The Sn atom seems to form the strongest bonds within the tetrel family. It is most effective in the context of a -SnF3 group and a further enhancement is observed when a positive charge is placed on the receptor. Connection of the -SnF3 group to either an imidazolium or triazolium provides a strong halide receptor, which can be improved if its point of attachment is changed from the C to an N atom of either ring. Aromaticity of the ring offers no advantage nor is a cyclic system superior to a simple alkyl amine of any chain length. Placing a pair of -SnF3 groups on a single molecule to form a bipodal dicationic receptor with two tetrel bonds enhances the binding, but falls short of a simple doubling. These two tetrel groups can be placed on opposite ends of an alkyl diamine chain of any length although SnF3+NH2(CH2nNH2SnF3+ with n between 2 and 4 seems to offer the strongest halide binding. Of the various anions tested, OH− binds most strongly: OH− > F− > Cl− > Br− > I−. The binding energy of the larger NO3− and HCO3− anions is more dependent upon the charge of the receptor. This pattern translates into very strong selectivity of binding one anion over another. The tetrel-bonding receptors bind far more strongly to each anion than an equivalent number of K+ counterions, which leads to equilibrium ratios in favor of the former of many orders of magnitude.

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

    International Nuclear Information System (INIS)

    Tang Aiwei; Wang Yu; Ye Haihang; Zhou Chao; Yang Chunhe; Li Xu; Peng Hongshang; Zhang Fujun; Hou Yanbing; Teng Feng

    2013-01-01

    A one-step colloidal process has been adopted to prepare silver (Ag) and silver sulfide (Ag 2 S) 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 Ag 2 S 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 Ag 2 S 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)

  15. 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

    2015-07-03

    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. Copyright © 2015, American Association for the Advancement of Science.

  16. Communication: Site-selective bond excision of adenine upon electron transfer

    Science.gov (United States)

    Cunha, T.; Mendes, M.; Ferreira da Silva, F.; Eden, S.; García, G.; Limão-Vieira, P.

    2018-01-01

    This work demonstrates that selective excision of hydrogen atoms at a particular site of the DNA base adenine can be achieved in collisions with electronegative atoms by controlling the impact energy. The result is based on analysing the time-of-flight mass spectra yields of potassium collisions with a series of labeled adenine derivatives. The production of dehydrogenated parent anions is consistent with neutral H loss either from selective breaking of C-H or N-H bonds. These unprecedented results open up a new methodology in charge transfer collisions that can initiate selective reactivity as a key process in chemical reactions that are dominant in different areas of science and technology.

  17. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1976-01-01

    Research progress is reported in programs on fuel-salt chemistry, properties of compounds in the Li--Te system, Te spectroscopy UF 4 --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--BeF 2 --ThF 4 for Fe and analysis of LiF--BeF--ThF 4 for Te

  18. Complex chemistry

    International Nuclear Information System (INIS)

    Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon

    2006-06-01

    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  19. Coulombic Interaction in Finnish Middle School Chemistry: A Systemic Perspective on Students' Conceptual Structure of Chemical Bonding

    Science.gov (United States)

    Joki, Jarkko; Lavonen, Jari; Juuti, Kalle; Aksela, Maija

    2015-01-01

    The aim of this study was to design a novel and holistic way to teach chemical bonding at the middle school level according to research on the teaching and learning of bonding. A further aim was to investigate high achieving middle school students' conceptual structures concerning chemical bonding by using a systemic perspective. Students in one…

  20. Selective Hydrogen Atom Abstraction through Induced Bond Polarization: Direct α-Arylation of Alcohols through Photoredox, HAT, and Nickel Catalysis.

    Science.gov (United States)

    Twilton, Jack; Christensen, Melodie; DiRocco, Daniel A; Ruck, Rebecca T; Davies, Ian W; MacMillan, David W C

    2018-05-04

    The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation method for the selective functionalization of alcohol α-hydroxy C-H bonds. This approach employs zinc-mediated alcohol deprotonation to activate α-hydroxy C-H bonds while simultaneously suppressing C-O bond formation by inhibiting the formation of nickel alkoxide species. The use of Zn-based Lewis acids also deactivates other hydridic bonds such as α-amino and α-oxy C-H bonds. This approach facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3-step synthesis of the drug Prozac exemplifies the utility of this new method. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. 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

    2015-11-09

    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.

  2. Hydrogen bond based smart polymer for highly selective and tunable capture of multiply phosphorylated peptides.

    Science.gov (United States)

    Qing, Guangyan; Lu, Qi; Li, Xiuling; Liu, Jing; Ye, Mingliang; Liang, Xinmiao; Sun, Taolei

    2017-09-06

    Multisite phosphorylation is an important and common mechanism for finely regulating protein functions and subsequent cellular responses. However, this study is largely restricted by the difficulty to capture low-abundance multiply phosphorylated peptides (MPPs) from complex biosamples owing to the limitation of enrichment materials and their interactions with phosphates. Here we show that smart polymer can serve as an ideal platform to resolve this challenge. Driven by specific but tunable hydrogen bonding interactions, the smart polymer displays differential complexation with MPPs, singly phosphorylated and non-modified peptides. Importantly, MPP binding can be modulated conveniently and precisely by solution conditions, resulting in highly controllable MPP adsorption on material surface. This facilitates excellent performance in MPP enrichment and separation from model proteins and real biosamples. High enrichment selectivity and coverage, extraordinary adsorption capacities and recovery towards MPPs, as well as high discovery rates of unique phosphorylation sites, suggest its great potential in phosphoproteomics studies.Capture of low-abundance multiply phosphorylated peptides (MPPs) is difficult due to limitation of enrichment materials and their interactions with phosphates. Here the authors show, a smart polymer driven by specific but tunable hydrogen bonding interactions can differentially complex with MPPs, singly phosphorylated and non-modified peptides.

  3. 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.

  4. The use of ultrasmall iron(0) nanoparticles as catalysts for the selective hydrogenation of unsaturated C-C bonds.

    Science.gov (United States)

    Kelsen, Vinciane; Wendt, Bianca; Werkmeister, Svenja; Junge, Kathrin; Beller, Matthias; Chaudret, Bruno

    2013-04-28

    The performance of well-defined ultrasmall iron(0) nanoparticles (NPs) as catalysts for the selective hydrogenation of unsaturated C-C and C=X bonds is reported. Monodisperse iron nanoparticles of about 2 nm size are synthesized by the decomposition of {Fe(N[Si(CH3)3]2)2}2 under dihydrogen. They are found to be active for the hydrogenation of various alkenes and alkynes under mild conditions and weakly active for C=O bond hydrogenation.

  5. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    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 Te 2 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 NaBF 4 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, Na 3 CrF 6 and Na 5 Cr 3 F 14 , 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 Li 2 BeF 4 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 Fe 2+ and Cr 3+ and the determination of the U 3+ /U 4+ ratio in MSBR fuel salt. Similar studies were conducted with the NaBF 4 --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 NaBF 4 --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)

  6. An evaluation of selection criteria on primary water chemistry parameters for SMART

    International Nuclear Information System (INIS)

    Choi, B. S.; Kim, S. H.; Yun, J. H.; Bae, Y. Y.; Gee, S. G.

    2003-01-01

    The selection criteria on the primary water chemistry of SMART by comparing the chemical design features with those of the current operating PWRs is analyzed. The most essential differences in water chemistry between the PWRs and SMART reactor is characterized by the presence of boron in water. SMART is boron free reactor, and the ammonia is used as a pH reagent. In SMART reactor hydrogen gas is not added to the primary coolant, but is normally generated from the radiolysis of ammonia of the coolant passes through the core. Ammonia is added once per shift because SMART reactor has no letdown and charging system during power operation. Because of these competing processes, the concentrations of hydrogen, nitrogen and ammonia in the primary coolant are steady state concentrations, which depend on the decomposition/combination rate of ammonia. Ammonia chemistry in SMART reactor has many advantages in that no hydrogen gas injection is needed to control the dissolved oxygen in primary coolant because of spontaneous generation of hydrogen and nitrogen produced by the reaction of ammonia decomposition

  7. Chemistry for environmental scientists

    Energy Technology Data Exchange (ETDEWEB)

    Moeller, Detlev [Brandenburgische Technische Univ., Berlin (Germany). Lehrstuhl fuer Luftchemie und Luftreinhaltung

    2015-07-01

    Non-chemists in environmental sciences and engineering (e.g. physicists, biologists, ecologists, geographers, soil scientists, hydrologists, meteorologists, economists, engineers) need chemical basic knowledge for understanding chemical processes in the environment. This book focuses on general and fundamental chemistry (including required physics) such as properties and bonding of matter, chemical kinetics and mechanisms, phase and chemical equilibrium, the basic features of air (gases), water (liquids) and soil (solids) and the most important substances and their reactions in the environment. Selected key environmental chemical processes are shortly characterised in the light of multi-component and multiphase chemistry. This book is also useful for chemists who are beginning work on environmental issues.

  8. Chemistry for environmental scientists

    International Nuclear Information System (INIS)

    Moeller, Detlev

    2015-01-01

    Non-chemists in environmental sciences and engineering (e.g. physicists, biologists, ecologists, geographers, soil scientists, hydrologists, meteorologists, economists, engineers) need chemical basic knowledge for understanding chemical processes in the environment. This book focuses on general and fundamental chemistry (including required physics) such as properties and bonding of matter, chemical kinetics and mechanisms, phase and chemical equilibrium, the basic features of air (gases), water (liquids) and soil (solids) and the most important substances and their reactions in the environment. Selected key environmental chemical processes are shortly characterised in the light of multi-component and multiphase chemistry. This book is also useful for chemists who are beginning work on environmental issues.

  9. Chemistry and kinetics of size-selected cobalt cluster cations at thermal energies. I. Reactions with CO

    Science.gov (United States)

    Guo, B. C.; Kerns, K. P.; Castleman, A. W., Jr.

    1992-06-01

    The chemistry and kinetics of size-selected Co+n cluster-ion (n=2-8) reactions with CO are studied using a selected ion drift tube affixed with a laser vaporization source operated under well-defined thermal conditions. All reactions studied in the present work are found to be association reactions. Their absolute rate constants, which are determined quantitatively, are found to have a strong dependence on cluster size. Similar to the cases of reactions with many other reactants such as H2 and CH4, Co+4 and Co+5 display a higher reactivity toward the CO molecule than do clusters of neighboring size. The multiple-collision conditions employed in the present work have enabled a determination of the maximum coordination number of CO molecules bound onto each Co+n cluster. It is found that the tetramer tends to bond 12 CO molecules, the pentamer 14 CO, hexamer 16 CO, and so on. The results are interpreted in terms of Lauher's calculation and the polyhedral skeletal electron pair theory. All the measured maximum coordination numbers correlate extremely well with the predictions of these theories, except for the trimer where the measured number is one CO less than the predicted value. The good agreement between experiment and theory enables one to gain some insight into the geometric structure of the clusters. Based on the present findings, the cobalt tetramer cation is interpreted to have a tetrahedral structure, the pentamer a trigonal bipyramid, and the hexamer an octahedral structure. Other cluster structures are also discussed.

  10. Comparison of the bond strength of ceramics to Co-Cr alloys made by casting and selective laser melting.

    Science.gov (United States)

    Lawaf, Shirin; Nasermostofi, Shahbaz; Afradeh, Mahtasadat; Azizi, Arash

    2017-02-01

    Considering the importance of metal-ceramic bond, the present study aimed to compare the bond strength of ceramics to cobalt-chrome (Co-Cr) alloys made by casting and selective laser melting (SLM). In this in-vitro experimental study, two sample groups were prepared, with one group comprising of 10 Co-Cr metal frameworks fabricated by SLM method and the other of 10 Co-Cr metal frameworks fabricated by lost wax cast method with the dimensions of 0.5 × 3 × 25 mm (following ISO standard 9693). Porcelain with the thickness of 1.1 mm was applied on a 3 × 8-mm central rectangular area of each sample. Afterwards, bond strengths of the samples were assessed with a Universal Testing Machine. Statistical analysis was performed with Kolmogorov-Smirnov test and T-test. Bond strength in the conventionally cast group equaled 74.94 ± 16.06 MPa, while in SLM group, it equaled 69.02 ± 5.77 MPa. The difference was not statistically significant ( P ≤ .05). The results indicated that the bond strengths between ceramic and Co-Cr alloys made by casting and SLM methods were not statistically different.

  11. Experimentally calibrated computational chemistry of tryptophan hydroxylase: Trans influence, hydrogen-bonding, and 18-electron rule govern O-2-activation

    DEFF Research Database (Denmark)

    Haahr, Lærke Tvedebrink; Kepp, Kasper Planeta; Boesen, Jane

    2010-01-01

    with the experimental value (0.25 mm/s) which we propose as the structure of the hydroxylating intermediate, with the tryptophan substrate well located for further reaction 3.5 Å from the ferryl group. Based on the optimized transition states, the activation barriers for the two paths (glu and his) are similar, so......Insight into the nature of oxygen activation in tryptophan hydroxylase has been obtained from density functional computations. Conformations of O2-bound intermediates have been studied with oxygen trans to glutamate and histidine, respectively. An O2-adduct with O2 trans to histidine (Ohis...... towards the cofactor and a more activated O–O bond (1.33 Å) than in Oglu (1.30 Å). It is shown that the cofactor can hydrogen bond to O2 and activate the O–O bond further (from 1.33 to 1.38 Å). The Ohis intermediate leads to a ferryl intermediate (Fhis) with an isomer shift of 0.34 mm/s, also consistent...

  12. Unveiling of novel regio-selective fatty acid double bond hydratases from Lactobacillus acidophilus involved in the selective oxyfunctionalization of mono- and di-hydroxy fatty acids.

    Science.gov (United States)

    Kim, Kyoung-Rok; Oh, Hye-Jin; Park, Chul-Soon; Hong, Seung-Hye; Park, Ji-Young; Oh, Deok-Kun

    2015-11-01

    The aim of this study is the first time demonstration of cis-12 regio-selective linoleate double-bond hydratase. Hydroxylation of fatty acids, abundant feedstock in nature, is an emerging alternative route for many petroleum replaceable products thorough hydroxy fatty acids, carboxylic acids, and lactones. However, chemical route for selective hydroxylation is still quite challenging owing to low selectivity and many environmental concerns. Hydroxylation of fatty acids by hydroxy fatty acid forming enzymes is an important route for selective biocatalytic oxyfunctionalization of fatty acids. Therefore, novel fatty acid hydroxylation enzymes should be discovered. The two hydratase genes of Lactobacillus acidophilus were identified by genomic analysis, and the expressed two recombinant hydratases were identified as cis-9 and cis-12 double-bond selective linoleate hydratases by in vitro functional validation, including the identification of products and the determination of regio-selectivity, substrate specificity, and kinetic parameters. The two different linoleate hydratases were the involved enzymes in the 10,13-dihydroxyoctadecanoic acid biosynthesis. Linoleate 13-hydratase (LHT-13) selectively converted 10 mM linoleic acid to 13S-hydroxy-9(Z)-octadecenoic acid with high titer (8.1 mM) and yield (81%). Our study will expand knowledge for microbial fatty acid-hydroxylation enzymes and facilitate the designed production of the regio-selective hydroxy fatty acids for useful chemicals from polyunsaturated fatty acid feedstocks. © 2015 Wiley Periodicals, Inc.

  13. Electrostatics in Chemistry

    Indian Academy of Sciences (India)

    fundamental concepts of electrostatics as applied to atoms and molecules. The electric ... chemistry, the chemistry of the covalent bond, deals with the structures ..... the position of an asteroid named Ceres ... World Scientific. Singapore, 1992.

  14. Frontiers in Gold Chemistry

    OpenAIRE

    Ahmed A. Mohamed

    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...

  15. 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

    moment, excites the molecule to a dissociative electronic state. We consider the HOD molecule which is ideal due to the local mode structure of the vibrational states. It is shown that selective and localized bond stretching can be created in simple laser fields. When such a nonstationary vibrating HOD...... molecule is photodissociated with a short laser pulse (~5 fs) complete selectivity between the channels H+OD and D+OH is observed over the entire absorption band covering these channels. The Journal of Chemical Physics is copyrighted by The American Institute of Physics....

  16. Organic chemistry

    International Nuclear Information System (INIS)

    2003-08-01

    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.

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

    KAUST Repository

    Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

    2015-01-01

    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

  18. 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.

  19. Selective control of reformed composition of n-heptane via plasma chemistry

    KAUST Repository

    Manoj Kumar Reddy, P.

    2016-08-23

    This paper presents experimental results for reforming n-heptane in a temperature-controlled dielectric barrier discharge reactor to show detailed chemical composition in the products and to propose a potential method to control the product composition. Reformed products of n-heptane and water mixture in an inert Ar feed could be identified as hydrogen, carbon monoxide, oxygenates, and various hydrocarbons, having a wide range of carbon numbers. To selectively increase production of short-chain hydrocarbons, Ar was replaced by CH4. An increased pool of methyl radicals, via plasma chemistry of CH4, might facilitate to stabilize intermediate alkyls (R) into RCH3, which successfully increased short-chain hydrocarbon concentration. When CO2 was supplied instead of Ar (to provide enriched OH and O radicals), significantly higher oxygenate concentrations were obtained through the stabilization of alkyls as ROH (alcohol), and RC([Formula presented])R′ (ketone). The use of methane and carbon dioxide as feed to tailor the products of plasma-assisted reforming of n-heptane with methyl (CH3), or O radicals, is successfully demonstrated in the presence of water vapor. Detailed product analysis, such as product selection, rates and energy efficiency using a gas chromatograph and a gas chromatography mass spectrometer, will be elaborated upon. © 2016 Elsevier Ltd

  20. 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

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

    OpenAIRE

    Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

    2015-01-01

    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 u...

  2. Combustion Chamber Fluid Dynamics and Hypergolic Gel Propellant Chemistry Simulations for Selectable Thrust Rocket Engines

    National Research Council Canada - National Science Library

    Nusca, Michael J; Chen, Chiung-Chu; McQuaid, Michael J

    2007-01-01

    .... Computational fluid dynamics is employed to model the chemically reacting flow within a system's combustion chamber, and computational chemistry is employed to characterize propellant physical and reactive properties...

  3. 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.

  4. Favoring the unfavored: Selective electrochemical nitrogen fixation using a reticular chemistry approach.

    Science.gov (United States)

    Lee, Hiang Kwee; Koh, Charlynn Sher Lin; Lee, Yih Hong; Liu, Chong; Phang, In Yee; Han, Xuemei; Tsung, Chia-Kuang; Ling, Xing Yi

    2018-03-01

    Electrochemical nitrogen-to-ammonia fixation is emerging as a sustainable strategy to tackle the hydrogen- and energy-intensive operations by Haber-Bosch process for ammonia production. However, current electrochemical nitrogen reduction reaction (NRR) progress is impeded by overwhelming competition from the hydrogen evolution reaction (HER) across all traditional NRR catalysts and the requirement for elevated temperature/pressure. We achieve both excellent NRR selectivity (~90%) and a significant boost to Faradic efficiency by 10 percentage points even at ambient operations by coating a superhydrophobic metal-organic framework (MOF) layer over the NRR electrocatalyst. Our reticular chemistry approach exploits MOF's water-repelling and molecular-concentrating effects to overcome HER-imposed bottlenecks, uncovering the unprecedented electrochemical features of NRR critical for future theoretical studies. By favoring the originally unfavored NRR, we envisage our electrocatalytic design as a starting point for high-performance nitrogen-to-ammonia electroconversion directly from water vapor-abundant air to address increasing global demand of ammonia in (bio)chemical and energy industries.

  5. Thermodynamics of natural selection III: Landauer's principle in computation and chemistry.

    Science.gov (United States)

    Smith, Eric

    2008-05-21

    This is the third in a series of three papers devoted to energy flow and entropy changes in chemical and biological processes, and their relations to the thermodynamics of computation. The previous two papers have developed reversible chemical transformations as idealizations for studying physiology and natural selection, and derived bounds from the second law of thermodynamics, between information gain in an ensemble and the chemical work required to produce it. This paper concerns the explicit mapping of chemistry to computation, and particularly the Landauer decomposition of irreversible computations, in which reversible logical operations generating no heat are separated from heat-generating erasure steps which are logically irreversible but thermodynamically reversible. The Landauer arrangement of computation is shown to produce the same entropy-flow diagram as that of the chemical Carnot cycles used in the second paper of the series to idealize physiological cycles. The specific application of computation to data compression and error-correcting encoding also makes possible a Landauer analysis of the somewhat different problem of optimal molecular recognition, which has been considered as an information theory problem. It is shown here that bounds on maximum sequence discrimination from the enthalpy of complex formation, although derived from the same logical model as the Shannon theorem for channel capacity, arise from exactly the opposite model for erasure.

  6. Orotidine-Containing RNA: Implications for the Hierarchical Selection (Systems Chemistry Emergence) of RNA.

    Science.gov (United States)

    Kim, Eun-Kyong; Martin, Vincent; Krishnamurthy, Ramanarayanan

    2017-09-12

    The prebiotic synthesis of canonical nucleobases from HCN is a cornerstone for the RNA world hypothesis. However, their role in the primordial pathways to RNA is still debated. The very same process starting from HCN also gives rise to orotic acid, which (via orotidine) plays a crucial role in extant biology in the de novo synthesis of uridine and cytidine, the informational base-pairs in RNA. However, orotidine itself is absent in RNA. Given the prebiotic and biological relevance of orotic acid vis-à-vis uracil, we investigated orotidine-containing RNA oligonucleotides and show that they have severely compromised base-pairing properties. While not unexpected, these results suggest that the emergence of extant RNA cannot just be a consequence of the plausible prebiotic formation of its chemical constituents/building blocks. In combination with other investigations on alternative prebiotic nucleobases, sugars, and linkers, these findings imply that the selection of the components of extant RNA occurred at a higher hierarchical level of an oligomer/polymer based on its functional properties-pointing to a systems chemistry emergence of RNA from a library of precursors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Selectivity of calixarene-bonded silica phases in HPLC: Description of special characteristics with a multiple term linear equation at different methanol concentrations.

    Science.gov (United States)

    Schneider, Christian; Jira, Thomas

    2010-10-01

    Retention and selectivity characteristics of different calixarene-, resorcinarene- and alkyl-bonded stationary phases are examined by analyzing a set of test solutes covering the main interactions (hydrophobic, steric, ionic, polar) that apply in HPLC. Therefore Dolan and Snyder's multiple term linear equation has been adapted to fit the properties of calixarene-bonded columns. The obtained parameters are used to describe retention and selectivity of the novel Caltrex(®) phases and to elucidate underlying mechanisms of retention. Here, differences of stationary phase characteristics at different methanol concentrations in the mobile phases are examined. Both selectivity and retention were found to depend on the methanol content. Differences of these dependencies were found for different stationary phases and interactions. The differences between common alkyl-bonded and novel calixarene-bonded phases increase with increasing methanol content.

  8. Evidence for porphyrins bound, via ester bonds, to the Messel oil shale kerogen by selective chemical degradation experiments

    Science.gov (United States)

    Huseby, B.; Ocampo, R.

    1997-09-01

    High amounts of nickel mono- and di-acid porphyrins were released from Messel oil shale kerogen (Eocene, Germany) by selective chemical degradation (acid and base hydrolysis). The released porphyrin fractions were quantified (UV-vis) and their constituents isolated and characterized at the molecular level (UV-vis, MS, NMR). The mono-acid porphyrin fraction released contained four compounds of similar abundance which arise from an obvious chlorophyll or bacteriochlorophyll precursor. The di-acid porphyrin fraction was, however, dominated by far by one compound, mesoporphyrin IX, which must have originated from heme-like precursors (heme, cytochromes, etc.). These results show unambigously that the released mono- and di-acid porphyrins were linked to the macromolecular kerogen network via ester bonds and suggest that precursor heme-like pigments could be selectively and/or more readily incorporated into the macromolecular kerogen network than precursor chlorophylls and bacteriochlorophylls.

  9. Evaluation of the mechanical properties and porcelain bond strength of cobalt-chromium dental alloy fabricated by selective laser melting.

    Science.gov (United States)

    Wu, Lin; Zhu, Haiting; Gai, Xiuying; Wang, Yanyan

    2014-01-01

    Limited information is available regarding the microstructure and mechanical properties of dental alloy fabricated by selective laser melting (SLM). The purpose of this study was to evaluate the mechanical properties of a cobalt-chromium (Co-Cr) dental alloy fabricated by SLM and to determine the correlation between its microstructure and mechanical properties and its porcelain bond strength. Five metal specimens and 10 metal ceramic specimens were fabricated to evaluate the mechanical properties of SLM Co-Cr dental alloy (SLM alloy) with a tensile test and its porcelain bond strength with a 3-point bending test. The relevant properties of the SLM alloy were compared with those of the currently used Co-Cr dental alloy fabricated with conventional cast technology (cast alloy). The Student t test was used to compare the results of the SLM alloy and the cast alloy (α=.05). The microstructure of the SLM alloy was analyzed with a metallographic microscope; the metal ceramic interface of the SLM porcelain bonded alloy was studied with scanning electron microscopy, energy dispersive x-ray spectroscopy, and an electron probe microanalyzer. Both the mean (standard deviation) yield strength (884.37 ± 8.96 MPa) and tensile strength (1307.50 ±10.65 MPa) of the SLM alloy were notably higher than yield strength (568.10 ± 30.94 MPa) and tensile strength (758.73 ± 25.85 MPa) of the currently used cast alloy, and the differences were significant (P.05). Microstructure analysis suggested that the SLM alloy had a dense and obviously orientated microstructure, which led to excellent mechanical properties. Analysis from scanning electron microscopy, energy dispersive x-ray spectroscopy, and the electron probe microanalyzer indicated that the SLM alloy had an intermediate layer with elemental interpenetration between the alloy and the porcelain, which resulted in an improved bonding interface. Compared with the currently used cast alloy, SLM alloy possessed improved mechanical

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

    Energy Technology Data Exchange (ETDEWEB)

    Vaithilingam, Jayasheelan, E-mail: Jayasheelan.Vaithilingam@nottingham.ac.uk [Additive Manufacturing and 3D Printing Research Group, EPSRC Centre for Innovative Manufacturing in Additive Manufacturing, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Prina, Elisabetta [School of Pharmacy, Centre for Biomolecular Sciences, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Goodridge, Ruth D.; Hague, Richard J.M. [Additive Manufacturing and 3D Printing Research Group, EPSRC Centre for Innovative Manufacturing in Additive Manufacturing, School of Engineering, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Edmondson, Steve [School of Materials, The University of Manchester, Manchester M13 9PL (United Kingdom); Rose, Felicity R.A.J. [School of Pharmacy, Centre for Biomolecular Sciences, The University of Nottingham, Nottingham NG7 2RD (United Kingdom); Christie, Steven D.R. [Department of Chemistry, Loughborough University, Loughborough LE11 3TU (United Kingdom)

    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 ± 3.7 μm. 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. - Highlights: • Surface chemistry of selective laser melted (SLM) Ti6Al4V parts was compared with conventionally forged Ti6Al4V parts. • The surface elemental compositions of the SLM as-fabricated surfaces were significantly different to the forged surface. • Surface oxide-layer of the SLM as-fabricated was thicker than the polished SLM surfaces and the forged Ti6Al4V surfaces.

  11. Selective peptide bond hydrolysis of cysteine peptides in the presence of Ni(II) ions.

    Science.gov (United States)

    Protas, Anna Maria; Bonna, Arkadiusz; Kopera, Edyta; Bal, Wojciech

    2011-01-01

    Recently, we described a sequence-specific R1-(Ser/Thr) peptide bond hydrolysis reaction in peptides of a general sequence R1-(Ser/Thr)-Xaa-His-Zaa-R, which occurs in the presence of Ni(II) ions [A. Krężel, E. Kopera, A. M. Protas, A. Wysłouch-Cieszyńska, J. Poznański, W. Bal, J. Am. Chem. Soc. 132 (2010) 3355-3366]. In this study we explored the possibility of substituting the Ser/Thr and the His residues, necessary for the reaction to occur according to the Ni(II)-assisted acyl shift reaction mechanism, with Cys residues. We tested this concept by synthesizing three homologous peptides: R1-Ser-Arg-Cys-Trp-R2, R1-Cys-Arg-His-Trp-R2, and R1-Cys-Arg-Cys-Trp-R2, and the R1-Ser-Arg-His-Trp-R2 peptide as comparator (R1 and R2 were CH3CO-Gly-Ala and Lys-Phe-Leu-NH2, respectively). We studied their hydrolysis in the presence of Ni(II) ions, under anaerobic conditions and in the presence of TCEP as a thiol group antioxidant. We measured hydrolysis rates using HPLC and identified products of reaction using electrospray mass spectrometry. Potentiometry and UV-vis spectroscopy were used to assess Ni(II) complexation. We demonstrated that Ni(II) is not compatible with the Cys substitution of the Ser/Thr acyl acceptor residue, but the substitution of the Ni(II) binding His residue with a Cys yields a peptide susceptible to Ni(II)-related hydrolysis. The relatively high activity of the R1-Ser-Arg-Cys-Trp-R2 peptide at pH 7.0 suggests that this peptide and its Cys-containing analogs might be useful in practical applications of Ni(II)-dependent peptide bond hydrolysis. Copyright © 2010 Elsevier Inc. All rights reserved.

  12. 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. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

  13. Lifecycle comparison of selected Li-ion battery chemistries under grid and electric vehicle duty cycle combinations

    Science.gov (United States)

    Crawford, Alasdair J.; Huang, Qian; Kintner-Meyer, Michael C. W.; Zhang, Ji-Guang; Reed, David M.; Sprenkle, Vincent L.; Viswanathan, Vilayanur V.; Choi, Daiwon

    2018-03-01

    Li-ion batteries are expected to play a vital role in stabilizing the electrical grid as solar and wind generation capacity becomes increasingly integrated into the electric infrastructure. This article describes how two different commercial Li-ion batteries based on LiNi0.8Co0.15Al0.05O2 (NCA) and LiFePO4 (LFP) chemistries were tested under grid duty cycles recently developed for two specific grid services: (1) frequency regulation (FR) and (2) peak shaving (PS) with and without being subjected to electric vehicle (EV) drive cycles. The lifecycle comparison derived from the capacity, round-trip efficiency (RTE), resistance, charge/discharge energy, and total used energy of the two battery chemistries are discussed. The LFP chemistry shows better stability for the energy-intensive PS service, while the NCA chemistry is more conducive to the FR service under the operating regimes investigated. The results can be used as a guideline for selection, deployment, operation, and cost analyses of Li-ion batteries used for different applications.

  14. Hydrogen-bond-driven electrophilic activation for selectivity control: scope and limitations of fluorous alcohol-promoted selective formation of 1,2-disubstituted benzimidazoles and mechanistic insight for rationale of selectivity.

    Science.gov (United States)

    Chebolu, Rajesh; Kommi, Damodara N; Kumar, Dinesh; Bollineni, Narendra; Chakraborti, Asit K

    2012-11-16

    Hydrogen-bond-driven electrophilic activation for selectivity control during competitive formation of 1,2-disubstituted and 2-substituted benzimidazoles from o-phenylenediamine and aldehydes is reported. The fluorous alcohols trifluoroethanol and hexafluoro-2-propanol efficiently promote the cyclocondensation of o-phenylenediamine with aldehydes to afford selectively the 1,2-disubstituted benzimidazoles at rt in short times. A mechanistic insight is invoked by NMR, mass spectrometry, and chemical studies to rationalize the selectivity. The ability of the fluorous alcohols in promoting the reaction and controlling the selectivity can be envisaged from their better hydrogen bond donor (HBD) abilities compared to that of the other organic solvents as well as of water. Due to the better HBD values, the fluorous alcohols efficiently promote the initial bisimine formation by electrophilic activation of the aldehyde carbonyl. Subsequently the hydrogen-bond-mediated activation of the in situ-formed bisimine triggers the rearrangement via 1,3-hydride shift to form the 1,2-disubstituted benzimidazoles.

  15. Selected chapters from general chemistry in physics teaching with the help of e - learning

    Science.gov (United States)

    Feszterová, Melánia

    2017-01-01

    Education in the field of natural disciplines - Mathematics, Physics, Chemistry, Ecology and Biology takes part in general education at all schools on the territory of Slovakia. Its aim is to reach the state of balanced development of all personal characteristics of pupils, to teach them correctly identify and analyse problems, propose solutions and above all how to solve the problem itself. High quality education can be reached only through the pedagogues who have a good expertise knowledge, practical experience and high level of pedagogical abilities. The teacher as a disseminator of natural-scientific knowledge should be not only well-informed about modern tendencies in the field, but he/she also should actively participate in project tasks This is the reason why students of 1st year of study (bachelor degree) at the Department of Physics of Constantine the Philosopher University in Nitra attend lectures in the frame of subject General Chemistry. In this paper we present and describe an e - learning course called General Chemistry that is freely accessible to students. One of the aims of this course is to attract attention towards the importance of cross-curricular approach which seems to be fundamental in contemporary natural-scientific education (e.g. between Physics and Chemistry). This is why it is so important to implement a set of new topics and tasks that support development of abilities to realise cross-curricular goals into the process of preparation of future teachers of Physics.

  16. Efficient and Selective Chemical Labeling of Electrochemically Generated Peptides Based on Spirolactone Chemistry

    NARCIS (Netherlands)

    Zhang, Tao; Niu, Xiaoyu; Yuan, Tao; Tessari, Marco; de Vries, Marcel P.; Permentier, Hjalmar P.; Bischoff, Rainer

    2016-01-01

    Specific digestion of proteins is an essential step for mass spectrometry-based proteomics, and the chemical labeling of the resulting peptides is often used for peptide enrichment or the introduction of desirable tags. Cleavage of the peptide bond following electrochemical oxidation of Tyr or Trp

  17. Alkane Activation at Ambient Temperatures: Unusual Selectivities, C-C, C-H Bond Scission versus C-C Bond Coupling

    NARCIS (Netherlands)

    Trionfetti, C.; Agiral, A.; Gardeniers, Johannes G.E.; Lefferts, Leonardus; Seshan, Kulathuiyer

    2008-01-01

    Activating bonds: A cold plasma generated by dielectric barrier discharge in a microreactor converts alkanes (C1–C3) at atmospheric pressure. Large amounts of products with higher molecular weight than the starting hydrocarbons are observed showing that C-H activation at lower T favourably leads to

  18. Selective bond cleavage in potassium collisions with pyrimidine bases of DNA

    OpenAIRE

    Almeida, Diogo; Ferreira da Silva, F.; García, Gustavo; Limão-Vieira, P.

    2013-01-01

    Portuguese Foundation for Science and Technology (FCT-MEC) (SFRH/BD/61645/2009) FCT-MEC (PEst-OE/FIS/UI0068/2011) Spanish Ministerio de Economia y Competitividad (FIS 2009-10245; SFRH/BPD/68979/2010) Electron transfer in alkali-molecule collisions to gas phase thymine and uracil yielding H- formation is selectively controlled in the energy range between 5.3 and 66.1 eV. By tuning the collision energy, electron transfer from the alkali to partly deuterated thymine, methylated thymine at the...

  19. Click Chemistry in Complex Mixtures: Bioorthogonal Bioconjugation

    Science.gov (United States)

    McKay, Craig S.; Finn, M.G.

    2014-01-01

    The selective chemical modification of biological molecules drives a good portion of modern drug development and fundamental biological research. While a few early examples of reactions that engage amine and thiol groups on proteins helped establish the value of such processes, the development of reactions that avoid most biological molecules so as to achieve selectivity in desired bond-forming events has revolutionized the field. We provide an update on recent developments in bioorthogonal chemistry that highlights key advances in reaction rates, biocompatibility, and applications. While not exhaustive, we hope this summary allows the reader to appreciate the rich continuing development of good chemistry that operates in the biological setting. PMID:25237856

  20. Determination of selected azaarenes in water by bonded-phase extraction and liquid chromatography

    Science.gov (United States)

    Steinheimer, T.R.; Ondrus, M.G.

    1986-01-01

    A method for the rapid and simple quantitative determination of quinoline, isoquinoline, and five selected three-ring azaarenes in water has been developed. The azaarene fraction is separated from its carbon analogues on n-octadecyl packing material by edition with acidified water/acetonitrile. Concentration as great as 1000-fold is achieved readily. Instrumental analysis involves high-speed liquid chromatography on flexible-walled, wide-bore columns with fluorescence and ultraviolet detection at several wavelengths employing filter photometers in series. Method-validation data is provided as azaarene recovery efficiency from fortified samples. Distilled water, river water, contaminated ground water, and secondary-treatment effluent have been tested. Recoveries at part-per-billion levels are nearly quantitative for the three-ring compounds, but they decrease for quinoline and isoquinoline. ?? 1986 American Chemical Society.

  1. 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.

  2. Selected scientific articles. (Investigations in the field of hydrides chemistry and mineral raw materials processing)

    International Nuclear Information System (INIS)

    Mirsaidov, U.M.

    2013-01-01

    Articles, included in the present book are covering period 1977-2013 y. The main scientific articles in the field of power-consuming substances, mineral raw-materials and wastes reprocessing, including uranium industry wastes are collected. Scientific works on hydrogen chemistry which carried out basically bu U.M. Mirsaidov without co-authors are considered. These works are on aluminium hydrides and borohydrides lanthanides. Besides, author's popular-science articles on research carried out by Academy of Sciences during the period when he was the President of Academy of Sciences of the Republic of Tajikistan (1995-2005) are included. Mineral raw materials and wastes reprocessing results are given as well. The book is intended for engineer and technical staff, those working in the field of hydrogen chemistry, hydrometallurgy workers, engineering chemists as well as for PhD, post graduate students and students of appropriate profiles.

  3. Impact of menstruation on select hematology and clinical chemistry variables in cynomolgus macaques.

    Science.gov (United States)

    Perigard, Christopher J; Parrula, M Cecilia M; Larkin, Matthew H; Gleason, Carol R

    2016-06-01

    In preclinical studies with cynomolgus macaques, it is common to have one or more females presenting with menses. Published literature indicates that the blood lost during menses causes decreases in red blood cell mass variables (RBC, HGB, and HCT), which would be a confounding factor in the interpretation of drug-related effects on clinical pathology data, but no scientific data have been published to support this claim. This investigation was conducted to determine if the amount of blood lost during menses in cynomolgus macaques has an effect on routine hematology and serum chemistry variables. Ten female cynomolgus macaques (Macaca fascicularis), 5 to 6.5 years old, were observed daily during approximately 3 months (97 days) for the presence of menses. Hematology and serum chemistry variables were evaluated twice weekly. The results indicated that menstruation affects the erythrogram including RBC, HGB, HCT, MCHC, MCV, reticulocyte count, RDW, the leukogram including neutrophil, lymphocyte, and monocyte counts, and chemistry variables, including GGT activity, and the concentrations of total proteins, albumin, globulins, and calcium. The magnitude of the effect of menstruation on susceptible variables is dependent on the duration of the menstrual phase. Macaques with menstrual phases lasting ≥ 7 days are more likely to develop changes in variables related to chronic blood loss. In preclinical toxicology studies with cynomolgus macaques, interpretation of changes in several commonly evaluated hematology and serum chemistry variables requires adequate clinical observation and documentation concerning presence and duration of menses. There is a concern that macaques with long menstrual cycles can develop iron deficiency anemia due to chronic menstrual blood loss. © 2016 American Society for Veterinary Clinical Pathology.

  4. Chemical composition of selected Kansas brines as an aid to interpreting change in water chemistry with depth

    Science.gov (United States)

    Dingman, R.J.; Angino, E.E.

    1969-01-01

    Chemical analyses of approximately 1,881 samples of water from selected Kansas brines define the variations of water chemistry with depth and aquifer age. The most concentrated brines are found in the Permian rocks which occupy the intermediate section of the geologic column of this area. Salinity decreases below the Permian until the Ordovician (Arbuckle) horizon is reached and then increases until the Precambrian basement rocks are reached. Chemically, the petroleum brines studied in this small area fit the generally accepted pattern of an increase in calcium, sodium and chloride content with increasing salinity. They do not fit the often-predicted trend of increases in the calcium to chloride ratio, calcium content and salinity with depth and geologic age. The calcium to chloride ratio tends to be asymptotic to about 0.2 with increasing chloride content. Sulfate tends to decrease with increasing calcium content. Bicarbonate content is relatively constant with depth. If many of the hypotheses concerning the chemistry of petroleum brines are valid, then the brines studied are anomolous. An alternative lies in accepting the thesis that exceptions to these hypotheses are rapidly becoming the rule and that indeed we still do not have a valid and general hypothesis to explain the origin and chemistry of petroleum brines. ?? 1969.

  5. Water chemistry in 179 randomly selected Swedish headwater streams related to forest production, clear-felling and climate.

    Science.gov (United States)

    Löfgren, Stefan; Fröberg, Mats; Yu, Jun; Nisell, Jakob; Ranneby, Bo

    2014-12-01

    From a policy perspective, it is important to understand forestry effects on surface waters from a landscape perspective. The EU Water Framework Directive demands remedial actions if not achieving good ecological status. In Sweden, 44 % of the surface water bodies have moderate ecological status or worse. Many of these drain catchments with a mosaic of managed forests. It is important for the forestry sector and water authorities to be able to identify where, in the forested landscape, special precautions are necessary. The aim of this study was to quantify the relations between forestry parameters and headwater stream concentrations of nutrients, organic matter and acid-base chemistry. The results are put into the context of regional climate, sulphur and nitrogen deposition, as well as marine influences. Water chemistry was measured in 179 randomly selected headwater streams from two regions in southwest and central Sweden, corresponding to 10 % of the Swedish land area. Forest status was determined from satellite images and Swedish National Forest Inventory data using the probabilistic classifier method, which was used to model stream water chemistry with Bayesian model averaging. The results indicate that concentrations of e.g. nitrogen, phosphorus and organic matter are related to factors associated with forest production but that it is not forestry per se that causes the excess losses. Instead, factors simultaneously affecting forest production and stream water chemistry, such as climate, extensive soil pools and nitrogen deposition, are the most likely candidates The relationships with clear-felled and wetland areas are likely to be direct effects.

  6. 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

  7. Recent advances in H-phosphonate chemistry. Part 1. H-phosphonate esters: synthesis and basic reactions.

    Science.gov (United States)

    Sobkowski, Michal; Kraszewski, Adam; Stawinski, Jacek

    2015-01-01

    This review covers recent progress in the preparation of H-phosphonate mono- and diesters, basic studies on mechanistic and stereochemical aspects of this class of phosphorus compounds, and their fundamental chemistry in terms of transformation of P-H bonds into P-heteroatom bonds. Selected recent applications of H-phosphonate derivatives in basic organic phosphorus chemistry and in the synthesis of biologically important phosphorus compounds are also discussed.

  8. 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.

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

    KAUST Repository

    Li, Peng; He, Yabing; Zhao, Yunfeng; Weng, Linhong; Wang, Hailong; Krishna, Rajamani A A; Wu, Hui; Zhou, Wei; O'Keeffe, Michael A.; Han, Yu; Chen, Banglin

    2014-01-01

    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.

  10. 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

    2016-03-08

    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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Student selection: are the school-leaving A-level grades in biology and chemistry important?

    Science.gov (United States)

    Green, A; Peters, T J; Webster, D J

    1993-01-01

    This study determined the relationships of grades in A-level biology and chemistry with examination success or failure during the medical course. By inspection of medical student records, A-level grades at entry to medical school and examination performance were obtained for 128 (91%) of the students who sat their final MBBCh examination at the University of Wales College of Medicine in June 1988. The majority, 92 (72%), completed their medical school careers with no professional examination failures; 15 failed examinations just in the period up to 2nd MB; 11 failed examinations in the clinical period only and 10 failed examinations in both periods. Whereas grade achieved in A-level chemistry was not associated with undergraduate examination performance, students with a grade A or B in A-level biology were less likely to have problems than the others (21% compared with 47%; the difference of 26% has a 95% confidence interval of 7% to 44%). Specifically, there appears to be a strong relationship between a low grade in biology and difficulties in the preclinical examinations. Moreover, for those who have difficulties at this stage, this association continues later in the course.

  12. 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

  13. Palladium-catalyzed meta-selective C-H bond activation with a nitrile-containing template: computational study on mechanism and origins of selectivity.

    Science.gov (United States)

    Yang, Yun-Fang; Cheng, Gui-Juan; Liu, Peng; Leow, Dasheng; Sun, Tian-Yu; Chen, Ping; Zhang, Xinhao; Yu, Jin-Quan; Wu, Yun-Dong; Houk, K N

    2014-01-08

    Density functional theory investigations have elucidated the mechanism and origins of meta-regioselectivity of Pd(II)-catalyzed C-H olefinations of toluene derivatives that employ a nitrile-containing template. The reaction proceeds through four major steps: C-H activation, alkene insertion, β-hydride elimination, and reductive elimination. The C-H activation step, which proceeds via a concerted metalation-deprotonation (CMD) pathway, is found to be the rate- and regioselectivity-determining step. For the crucial C-H activation, four possible active catalytic species-monomeric Pd(OAc)2, dimeric Pd2(OAc)4, heterodimeric PdAg(OAc)3, and trimeric Pd3(OAc)6-have been investigated. The computations indicated that the C-H activation with the nitrile-containing template occurs via a Pd-Ag heterodimeric transition state. The nitrile directing group coordinates with Ag while the Pd is placed adjacent to the meta-C-H bond in the transition state, leading to the observed high meta-selectivity. The Pd2(OAc)4 dimeric mechanism also leads to the meta-C-H activation product but with higher activation energies than the Pd-Ag heterodimeric mechanism. The Pd monomeric and trimeric mechanisms require much higher activation free energies and are predicted to give ortho products. Structural and distortion energy analysis of the transition states revealed significant effects of distortions of the template on mechanism and regioselectivity, which provided hints for further developments of new templates.

  14. Studies of technetium chemistry. Pt.8. The regularities of the bond length and configuration of rhenium and technetium complexes in crystals

    International Nuclear Information System (INIS)

    Liu Guozheng; Liu Boli

    1995-01-01

    Some bond length regularities in MO 6 , MO-4, MX 5 α and MX 4 αβ moieties of technetium and rhenium compounds are summarized and rationalized by cavity model. The chemical properties of technetium and rhenium are so similar that their corresponding complexes have almost the same configuration and M-X bond lengths when they are in cavity-controlled state. Technetium and Rhenium combine preferably with N, O, F, S, Cl and Br when they are in higher oxidation states (>3), but preferably with P, Se etc. when they are in lower oxidation states ( 4 αβ is approximately constant; (2) the average M-X bond length of MX 6 varies moderately with the oxidation state of M; (3) the bond length of M-X trans to M-α in MX 5 α has a linear relationship with the angle

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

    Energy Technology Data Exchange (ETDEWEB)

    Vechiato-Filho, Aljomar José, E-mail: aljomarvechiatoflo@gmail.com [Department of Dental Materials and Prosthodontics, Aracatuba Dental School, Univ. Estadual Paulista — UNESP, Aracatuba, Sao Paulo (Brazil); Silva Vieira Marques, Isabella da [Department of Prosthodontics and Periodontology, Piracicaba Dental School, University of Campinas (UNICAMP), Piracicaba, Sao Paulo (Brazil); Santos, Daniela Micheline dos [Department of Dental Materials and Prosthodontics, Aracatuba Dental School, Univ. Estadual Paulista — UNESP, Aracatuba, Sao Paulo (Brazil); Oliveira Matos, Adaias [Department of Prosthodontics and Periodontology, Piracicaba Dental School, University of Campinas (UNICAMP), Piracicaba, Sao Paulo (Brazil); Rangel, Elidiane Cipriano; Cruz, Nilson Cristino da [Laboratory of Technological Plasmas (LaPTec), Engineering College, Univ. Estadual Paulista — UNESP, Sorocaba, Sao Paulo (Brazil); Barão, Valentim Adelino Ricardo [Department of Prosthodontics and Periodontology, Piracicaba Dental School, University of Campinas (UNICAMP), Piracicaba, Sao Paulo (Brazil)

    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. - Highlights: • We tested the bond strength between two widely used materials in dentistry (acrylic and titanium). • We performed an innovative surface treatment with nonthermal plasma. • Increasing adhesion will avoid complications of full-arch implant-retained prostheses.

  16. Selective Acid Etching Improves the Bond Strength of Universal Adhesive to Sound and Demineralized Enamel of Primary Teeth.

    Science.gov (United States)

    Antoniazzi, Bruna Feltrin; Nicoloso, Gabriel Ferreira; Lenzi, Tathiane Larissa; Soares, Fabio Zovico Maxnuck; Rocha, Rachel de Oliveira

    To evaluate the influence of enamel condition and etching strategy on bond strength of a universal adhesive in primary teeth. Thirty-six primary molars were randomly assigned to six groups (n = 6) according to the enamel condition (sound [S] and demineralized [DEM]/cariogenic challenge by pH cycling prior to restorative procedures) and adhesive system (Scotchbond Universal Adhesive [SBU]) used in either etch-and-rinse (ER) or selfetching (SE) mode, with Clearfil SE Bond as the self-etching control. The adhesives were applied to flat enamel surfaces and composite cylinders (0.72 mm2) were built up. After 24-h storage in water, specimens were subjected to the microshear test. Bond strength (MPa) data were analyzed using two-way ANOVA and Tukey's post-hoc tests (α = 0.05). Significant differences were found considering the factors adhesive system (p = 0.003) and enamel condition (p = 0.001). Demineralized enamel negatively affected the bond strength, with μSBS values approximately 50% lower than those obtained for sound enamel. SBU performed better in etch-and-rinse mode, and the bond strength found for SBU applied in self-etching mode was similar to that of CSE. Enamel etching with phosphoric acid improves the bond strength of a universal adhesive system to primary enamel. Demineralized primary enamel results in lower bond strength.

  17. Selectivity of calixarene-bonded silica-phases in HPLC: description of special characteristics with a multiple term linear equation at two different pH-values.

    Science.gov (United States)

    Schneider, Christian; Meyer, Rüdiger; Jira, Thomas

    2008-09-01

    Six different calixarene-bonded phases were characterized by analyzing 36 and 26 solutes at pH 3 and 7, respectively. Dolan and Snyder's multiple term linear equation was used to correlate retention factors k' to parameters of the solutes and columns. The column parameters have been related to molecular properties of the stationary phases and new suggestions were made for the interpretation of steric selectivity. Ionic and polar interactions have been found dependent on pH value, while steric interactions are less dependent and hydrophobic interactions remain unchanged. Distinct differences of the supported interactions were confirmed between the calixarene-bonded and the common alkyl-bonded silicas. By use of the parameters, values of k' can be estimated with an average deviation of 2.50 and 7.92% at low and neutral pH-value, respectively.

  18. Quantification of the selective activation of C--H bonds in short chain alkanes: The reactivity of ethane, propane, isobutane, n-butane, and neopentane on Ir(111)

    International Nuclear Information System (INIS)

    Johnson, D.F.; Weinberg, W.H.

    1995-01-01

    The initial probabilities of precursor-mediated, dissociative chemisorption of the saturated hydrocarbons 13 C-labeled ethane, propane, isobutane, n-butane, and neopentane on the close-packed Ir(111) surface have been measured. The selective activation of primary (1 degree), secondary (2 degree), and tertiary (3 degree) C--H bonds has been quantified by examining the reactivities of the selectively deuterated isotopomers of propane, C 3 H 8 , CH 3 CD 2 CH 3 , and C 3 D 8 , and of isobutane, (CH 3 ) 3 CH, (CH 3 ) 3 CD, and (CD 3 ) 3 CH. With respect to the bottom of the physically adsorbed well for each hydrocarbon, the apparent C--H bond activation energies have been found to be 10.4±0.3 kcal/mol (ethane), 11.4±0.3 kcal/mol (propane), 11.5±0.3 kcal/mol (n-butane), 11.3±0.3 kcal/mol (i-butane), and 11.3±0.3 kcal/mol (neopentane). For all the alkanes examined, the ratios of the preexponential factors of the rate coefficients of reaction and desorption are 1x10 -2 . The C--D bond activation energies are higher than the corresponding C--H bond activation energies by 480 cal/mol (ethane), 630 cal/mol (propane), and 660 cal/mol (i-butane). By analyzing the primary kinetic isotope effects for the selectively deuterated isotopomers of propane and isobutane, the 2 degree C--H bond activation energy is found to be 310±160 cal/mol less than the 1 degree C--H bond activation energy on this surface, and similarly, 3 degree C--H bond cleavage is less by 80±70 cal/mol. The quantification of the branching ratios within the C--H bond activation channel for propane and isobutane on this surface shows that the formation of 1 degree-alkyl intermediates is, in general, favored over the formation of either 2 degree- or 3 degree-alkyl intermediates. (Abstract Truncated)

  19. Unusual bonding and properties in main group element chemistry: rational synthesis, characterization, and experimental electron density determination of mixed-valent tetraphosphetes.

    Science.gov (United States)

    Breuers, Verena; Lehmann, Christian W; Frank, Walter

    2015-03-16

    Five dispirocyclic λ(3),λ(5)-tetraphosphetes [{R2Si(NR(1))(NR(2))P2}2] (R(1) = R(2) and R(1) ≠ R(2)) are easily prepared in almost quantitative yields via photolysis of the respective bis(trimethylsilyl)phosphanyldiazaphosphasiletidines with intense visible light. These deep-yellow low-coordinate phosphorus compounds can be considered as the first higher congeners of the well-known cyclodiphosphazenes. The tetraphosphetes are remarkably stable in air and show unexpected molecular properties related to the unique bonding situation of the central four-π-electron four-membered phosphorus ring. The extent of rhombic distortion of the central P4 ring is remarkable due to an unusually acute angle at the σ(2)-phosphorus atoms. All of the P-P bonds are approximately equal in length. The distances are in the middle of the range given by phosphorus single and double bonds. The anisotropic absorption of visible light that can easily be observed in the case of the yellow/colorless dichroic crystals of [{Me2Si(NtBu)(NtBu)P2}2] and the exceptional (31)P NMR chemical shift of the σ(2)-phosphorus atoms are the most remarkable features of the λ(3),λ(5)-tetraphosphetes. In the case of [{Me2Si(NtBu)(NtBu)P2}2], the Hansen-Coppens multipole model is applied to extract the electron density from high-resolution X-ray diffraction data obtained at 100 K. Static deformation density and topological analysis reveal a unique bonding situation in the central unsaturated P4 fragment characterized by polar σ-bonding, pronounced out-of-ring non-bonding lone pair density on the σ(2)-phosphorus atoms, and an additional non-classical three-center back-bonding contribution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Photodissociation of quantum state-selected diatomic molecules yields new insight into ultracold chemistry

    Science.gov (United States)

    McDonald, Mickey; McGuyer, Bart H.; Lee, Chih-Hsi; Apfelbeck, Florian; Zelevinsky, Tanya

    2016-05-01

    When a molecule is subjected to a sufficiently energetic photon it can break apart into fragments through a process called ``photodissociation''. For over 70 years this simple chemical reaction has served as a vital experimental tool for acquiring information about molecular structure, since the character of the photodissociative transition can be inferred by measuring the 3D photofragment angular distribution (PAD). While theoretical understanding of this process has gradually evolved from classical considerations to a fully quantum approach, experiments to date have not yet revealed the full quantum nature of this process. In my talk I will describe recent experiments involving the photodissociation of ultracold, optical lattice-trapped, and fully quantum state-resolved 88Sr2 molecules. Optical absorption images of the PADs produced in these experiments reveal features which are inherently quantum mechanical in nature, such as matter-wave interference between output channels, and are sensitive to the quantum statistics of the molecular wavefunctions. The results of these experiments cannot be predicted using quasiclassical methods. Instead, we describe our results with a fully quantum mechanical model yielding new intuition about ultracold chemistry.

  1. 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.

  2. 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.

  3. Communication: Reactivity borrowing in the mode selective chemistry of H + CHD3 → H2 + CD3

    Science.gov (United States)

    Ellerbrock, Roman; Manthe, Uwe

    2017-12-01

    Quantum state-resolved reaction probabilities for the H + CHD3 → H2 + CD3 reaction are calculated by accurate full-dimensional quantum dynamics calculations using the multi-layer multi-configurational time-dependent Hartree approach and the quantum transition state concept. Reaction probabilities of various ro-vibrational states of the CHD3 reactant are investigated for vanishing total angular momentum. While the reactivity of the different vibrational states of CHD3 mostly follows intuitive patterns, an unusually large reaction probability is found for CHD3 molecules triply excited in the CD3 umbrella-bending vibration. This surprising reactivity can be explained by a Fermi resonance-type mixing of the single CH-stretch excited and the triple CD3 umbrella-bend excited vibrational states of CHD3. These findings show that resonant energy transfer can significantly affect the mode-selective chemistry of CHD3 and result in counter-intuitive reactivity patterns.

  4. A remarkable enhancement of selectivity towards versatile analytes by a strategically integrated H-bonding site containing phase.

    Science.gov (United States)

    Mallik, Abul K; Qiu, Hongdeng; Kuwahara, Yutaka; Takafuji, Makoto; Ihara, Hirotaka

    2015-09-28

    A double β-alanylated L-glutamide-derived organic phase has been newly designed and synthesized in such a way that integrated H-bonding (interaction) sites make it very suitable for the separation of versatile analytes, including shape-constrained isomers, and nonpolar, polar and basic compounds. The β-alanine residues introduced into two long-chain alkyl group moieties provide ordered polar groups through H-bonding among the amide groups.

  5. Supramolecular Chemistry of Selective Anion Recognition for Anions of Environmental Relevance

    International Nuclear Information System (INIS)

    Bowman-James, K.; Wilson, G.; Moyer, B. A.

    2004-01-01

    This project involves the design and synthesis of receptors for oxoanions of environmental importance, including emphasis on high level and low activity waste. Target anions have included primarily oxoanions and a study of the basic concepts behind selective binding of target anions. A primary target has been sulfate because of its deleterious influence on the vitrification of tank wastes

  6. 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.

  7. Effects of selected water chemistry variables on copper pitting propagation in potable water

    International Nuclear Information System (INIS)

    Ha Hung; Taxen, Claes; Williams, Keith; Scully, John

    2011-01-01

    Highlights: → The effects of water composition on pit propagation kinetics on Cu were separated from pit initiation and stabilization using the artificial pit method in a range of dilute HCO 3 - , SO 4 2- and Cl - -containing waters. → The effective polarization and Ohmic resistance of pits were lower in SO4 2- -containing solutions and greater in Cl - -containing solutions. → Relationship between the solution composition and the corrosion product identity and morphology were found. → These, in turn controlled the corrosion product Ohmic resistance and subsequently the pit growth rate. - Abstract: The pit propagation behavior of copper (UNS C11000) was investigated from an electrochemical perspective using the artificial pit method. Pit growth was studied systematically in a range of HCO 3 - , SO 4 2- and Cl - containing-waters at various concentrations. Pit propagation was mediated by the nature of the corrosion products formed both inside and over the pit mouth (i.e., cap). Certain water chemistry concentrations such as those high in sulfate were found to promote fast pitting that could be sustained over long times at a fixed applied potential but gradually stifled in all but the lowest concentration solutions. In contrast, Cl - containing waters without sulfate ions resulted in slower pit growth and eventual repassivation. These observations were interpreted through understanding of the identity, amount and porosity of corrosion products formed inside and over pits. These factors controlled their resistive nature as characterized using electrochemical impedance spectroscopy. A finite element model (FEM) was developed which included copper oxidation kinetics, transport by migration and diffusion, Cu(I) and Cu(II) solid corrosion product formation and porosity governed by equilibrium thermodynamics and a saturation index, as well as pit current and depth of penetration. The findings of the modeling were in good agreement with artificial pit experiments

  8. Effect of La2O3 addition on interface chemistry between 4YSZ top layer and Ni based alloy bond coat in thermal barrier coating by EB PVD.

    Science.gov (United States)

    Park, Chan-Young; Yang, Young-Hwan; Kim, Seong-Won; Lee, Sung-Min; Kim, Hyung-Tae; Jang, Byung-Koog; Lim, Dae-Soon; Oh, Yoon-Suk

    2014-11-01

    The effect of a 5 mol% La2O3 addition on the forming behavior and compositional variation at interface between a 4 mol% Yttria (Y2O3) stabilized ZrO2 (4YSZ) top coat and bond coat (NiCrAlY) as a thermal barrier coating (TBC) has been investigated. Top coats were deposited by electron beam physical vapor deposition (EB PVD) onto a super alloy (Ni-Cr-Co-Al) substrate without pre-oxidation of the bond coat. Top coats are found to consist of dense columnar grains with a thin interdiffusion layer between metallic bond coats. In the as-received 4YSZ coating, a thin interdiffusion zone at the interface between the top and bond coats was found to consist of a Ni-Zr intermetallic compound with a reduced quantity of Y, Al or O elements. On the other hand, in the case of an interdiffusion area of 5 mol% La2O3-added 4YSZ coating, it was found that the complicated composition and structure with La-added YSZ and Ni-Al rich compounds separately. The thermal conductivity of 5 mol% La2O3-added 4YSZ coating (- 1.6 W/m x k at 1100 degrees C) was lower than a 4YSZ coating (- 3.2 W/m x k at 1100 degrees C) alone.

  9. Promotion Effect of Alkali Metal Hydroxides on Polymer-Stabilized Pd Nanoparticles for Selective Hydrogenation of C–C Triple Bonds in Alkynols

    OpenAIRE

    Nikoshvili, Linda Zh.; Bykov, Alexey V.; Khudyakova, Tatiana E.; Lagrange, Thomas; Héroguel, Florent; Luterbacher, Jeremy S.; Matveeva, Valentina G.; Sulman, Esther M.; Dyson, Paul J.; Kiwi-Minsker, Lioubov

    2017-01-01

    Postimpregnation of Pd nanoparticles (NPs) stabilized within hyper-cross-linked polystyrene with sodium or potassium hydroxides of optimal concentration was found to significantly increase the catalytic activity for the partial hydrogenation of the C–C triple bond in 2-methyl-3-butyn-2-ol at ambient hydrogen pressure. The alkali metal hydroxide accelerates the transformation of the residual Pd(II) salt into Pd(0) NPs and diminishes the reaction induction period. In addition, the selectivity t...

  10. Highly selective deuteration of pharmaceutically relevant nitrogen-containing heterocycles: a flow chemistry approach.

    Science.gov (United States)

    Ötvös, Sándor B; Mándity, István M; Fülöp, Ferenc

    2011-08-01

    A simple and efficient flow-based technique is reported for the catalytic deuteration of several model nitrogen-containing heterocyclic compounds which are important building blocks of pharmacologically active materials. A continuous flow reactor was used in combination with on-demand pressure-controlled electrolytic D(2) production. The D(2) source was D(2)O, the consumption of which was very low. The experimental set-up allows the fine-tuning of pressure, temperature, and flow rate so as to determine the optimal conditions for the deuteration reactions. The described procedure lacks most of the drawbacks of the conventional batch deuteration techniques, and additionally is highly selective and reproducible.

  11. 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.

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

    International Nuclear Information System (INIS)

    Bowman-James, Kristin

    2008-01-01

    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

  13. Probing into petroleum chemistry enterprise bonding and financing%石油化工企业债券融资探讨

    Institute of Scientific and Technical Information of China (English)

    李雯雯; 徐春骐

    2012-01-01

    作为资本密集型的国民经济基础行业,石化行业的资金约束是制约其经营发展和战略升级的主要因素之一。随着我国市场经济的发展和资本市场的不断完善,企业债券融资作为一种重要的直接融资方式,正以其广泛的资金来源、较低的融资成本等优势愈来愈受到各方重视。本文以1996~2011年间发债石化企业数据为基础,对石化企业融资结构和债券发行情况进行分析,对石化企业通过债券融资的优势进行阐述,同时结合现有法律法规及市场条件对石化企业债券发行及定价问题进行探讨。%Capital shortage is one of the main constraints on the business and strategic develpment of the national petrochemical industry which is capital-intensive.With the develpment of China's market economy and continuous improvement of capital markets,as an importan part of direct financing,corporate bond financing has received more and more attention for its wide range of funding sources,lower financing costs and other advantages.The number of petrochemical companies issuing bonds and size of bond financing has significantly improved in recent years with government policy support and high demand for broadening the financing channels.The status of petrochemical industry corporate bond financing,the advantages of bond financing,the practising of bond issuance will be discussed in this paper.

  14. Groundwater age and chemistry, and future nutrient loads for selected Rotorua Lakes catchments

    International Nuclear Information System (INIS)

    Morgenstern, U.; Reevers, R.R.; Daugney, C.J.; Cameron, S.; Gordon, D.

    2005-01-01

    Hydrochemical analysis and age dating of groundwater and groundwater-fed streams were carried out in the Lake Rotorua and Okareka catchments to assess the past and current states, and future trends in groundwater chemistry. The study was undertaken because of declining lake water quality due to observed increases in nutrient loads entering these lakes. THe hydrogeology of the Rotorua Lakes area can be described as a permeable pumiceous surface tephra layer that allows easy penetration of rainwater recharge to deeper rhyolite and ignimbrite aquifers. These aquifers are essentially unconfined and yield high volumes of groundwater that discharges to spring-fed streams or directly to the lake. The hydrochemistry of groundwaters is characterised by much lower concentrations of Ca, Mg and SO 4 and much higher concentrations of PO 4 -P and SiO 2 than other groundwaters in New Zealand. This chemical signature reflects the volcanic origin of the aquifer lithology. Because the aquifers in the Rotorua area have large water storage capacity there is a long residence time for nutrient-laden groundwater. It takes decades for the water after being recharged to reach the spring-fed streams and the lakes. The large groundwater bodies have therefore 'silently' been contaminated over decades, with the old pristine groundwater being progressively replaced by younger nutrient-laden water that will discharge to the spring-fed streams and finally to the lakes. This study involved age dating of springs, wells, and groundwater-fed streams to assess how long it takes for nutrient-enriched groundwater to travel from pastoral land to springs and streams, and to the lakes. Most of the springs and wells in the Lake Rotorua and Okareka catchments contained relatively old groundwaters, with mean residence times between 40 and >170 years (only two wells have younger water of 26 and 31 years mean residence time). This corresponds to young water fractions (water recharged within the last 55 years

  15. Physical Chemistry '98: Fourth International Conference on Fundamental and Applied Aspects of Physical Chemistry - Papers

    International Nuclear Information System (INIS)

    Ribnikar, S.; Anic, S.

    1998-01-01

    The proceedings has following chapters: Plenary lectures; Chemical Thermodynamics; Spectroscopy, Molecular Structures, Physical Chemistry of Plasma; Kinetics, Catalysis, Nonlinear Dynamics; Electrochemistry; Biophysical Chemistry, Photochemistry, Radiation Chemistry; Radiochemistry, Nuclear Chemistry; Solid State Physical Chemistry, Material Science; Macromolecular Physical Chemistry; Environmental Protection; Phase Boundaries; Complex Compounds; General Physical Chemistry. A separated abstract was prepared for each of the 20 papers selected from the three chapters: Biophysical Chemistry, Photochemistry, Radiation Chemistry; Radiochemistry, Nuclear Chemistry. and Environmental Protection. Refs and figs

  16. Mechanistic aspects of dinitrogen cleavage and hydrogenation to produce ammonia in catalysis and organometallic chemistry: relevance of metal hydride bonds and dihydrogen.

    Science.gov (United States)

    Jia, Hong-Peng; Quadrelli, Elsje Alessandra

    2014-01-21

    Dinitrogen cleavage and hydrogenation by transition-metal centers to produce ammonia is central in industry and in Nature. After an introductory section on the thermodynamic and kinetic challenges linked to N2 splitting, this tutorial review discusses three major classes of transition-metal systems (homogeneous, heterogeneous and biological) capable of achieving dissociation and hydrogenation of dinitrogen. Molecular complexes, solid-state Haber-Bosch catalytic systems, silica-supported tantalum hydrides and nitrogenase will be discussed. Emphasis is focused on the reaction mechanisms operating in the process of dissociation and hydrogenation of dinitrogen, and in particular on the key role played by metal hydride bonds and by dihydrogen in such reactions.

  17. Indoor Chemistry

    DEFF Research Database (Denmark)

    Weschler, Charles J.; Carslaw, Nicola

    2018-01-01

    This review aims to encapsulate the importance, ubiquity, and complexity of indoor chemistry. We discuss the many sources of indoor air pollutants and summarize their chemical reactions in the air and on surfaces. We also summarize some of the known impacts of human occupants, who act as sources...... and sinks of indoor chemicals, and whose activities (e.g., cooking, cleaning, smoking) can lead to extremely high pollutant concentrations. As we begin to use increasingly sensitive and selective instrumentation indoors, we are learning more about chemistry in this relatively understudied environment....

  18. 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.

  19. A theoretical investigation of the feasibility of Tannor-Rice type control: Application to selective bond breakage in gas-phase dihalomethanes

    DEFF Research Database (Denmark)

    Shu, Chuan-Cun; Rozgonyi, Tamas; Gonzalez, Leticia

    2012-01-01

    Within the math absorption band of CH2BrCl, we theoretically analyze the laser-induced control of the Br/Cl branching ratio, Br + CH2Cl ← CH2BrCl → CH2Br + Cl, with CH2BrCl initially in its vibrational ground state. For weak-field excitation, the Br/Cl branching ratio increases as a function of w......-Rice type laser control mechanism for selective bond breakage in CH2BrCl cannot take place without accompanying photoionization....

  20. From ketones to esters by a Cu-catalyzed highly selective C(CO)-C(alkyl) bond cleavage: aerobic oxidation and oxygenation with air.

    Science.gov (United States)

    Huang, Xiaoqiang; Li, Xinyao; Zou, Miancheng; Song, Song; Tang, Conghui; Yuan, Yizhi; Jiao, Ning

    2014-10-22

    The Cu-catalyzed aerobic oxidative esterification of simple ketones via C-C bond cleavage has been developed. Varieties of common ketones, even inactive aryl long-chain alkyl ketones, are selectively converted into esters. The reaction tolerates a wide range of alcohols, including primary and secondary alcohols, chiral alcohols with retention of the configuration, electron-deficient phenols, as well as various natural alcohols. The usage of inexpensive copper catalyst, broad substrate scope, and neutral and open air conditions make this protocol very practical. (18)O labeling experiments reveal that oxygenation occurs during this transformation. Preliminary mechanism studies indicate that two novel pathways are mainly involved in this process.

  1. Organic chemistry experiment

    International Nuclear Information System (INIS)

    Mun, Seok Sik

    2005-02-01

    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.

  2. Radiation chemistry

    International Nuclear Information System (INIS)

    Rodgers, F.; Rodgers, M.A.

    1987-01-01

    The contents of this book include: Interaction of ionizing radiation with matter; Primary products in radiation chemistry; Theoretical aspects of radiation chemistry; Theories of the solvated electron; The radiation chemistry of gases; Radiation chemistry of colloidal aggregates; Radiation chemistry of the alkali halides; Radiation chemistry of polymers; Radiation chemistry of biopolymers; Radiation processing and sterilization; and Compound index

  3. Advances in computational actinide chemistry in China

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Dongqi; Wu, Jingyi; Chai, Zhifang [Chinese Academy of Sciences, Beijing (China). Multidisciplinary Initiative Center; Su, Jing [Chinese Academy of Sciences, Shanghai (China). Div. of Nuclear Materials Science and Engineering; Li, Jun [Tsinghua Univ., Beijing (China). Dept. of Chemistry and Laboratory of Organic Optoelectronics and Molecular Engineering

    2014-04-01

    The advances in computational actinide chemistry made in China are reviewed. Several areas relevant to chemistry of actinides in gas, liquid, and solid phases have been explored. However, we limit the scope to selected contributions in the chemistry of molecular actinide systems in gas and liquid phases. These studies may be classified into two categories: treatment of relativistic effects, which cover the development of two- and four-component Hamiltonians and the optimization of relativistic pseudopotentials, and the applications of theoretical methods in actinide chemistry. The applications include (1) the electronic structures of actinocene, noble gas complexes, An-C multiple bonding compounds, uranyl and its isoelectronic species, fluorides and oxides, molecular systems with metal-metal bonding in their isolated forms (U{sub 2}, Pu{sub 2}) and in fullerene (U{sub 2} rate at C{sub 60}), and the excited states of actinide complexes; (2) chemical reactions, including oxidation, hydrolysis of UF{sub 6}, ligand exchange, reactivities of thorium oxo and sulfido metallocenes, CO{sub 2}/CS{sub 2} functionalization promoted by trivalent uranium complex; and (3) migration of actinides in the environment. A future outlook is discussed. (orig.)

  4. Complex cubic metallides AM{sub ∝6} (A=Ca, Sr; M=Zn, Cd, Hg). Synthesis, crystal chemistry and chemical bonding

    Energy Technology Data Exchange (ETDEWEB)

    Schwarz, Michael; Wendorff, Marco; Roehr, Caroline [Freiburg Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2017-09-01

    In a systematic synthetic, crystallographic and bond theoretical study, the stability ranges as well as the distribution of the isoelectronic late d-block elements Zn, Cd and Hg (M) in the polyanions of the YCd{sub 6}-type phases (Ca/Sr)Cd{sub 6} have been investigated. Starting from Ca(Cd/Hg){sub 6}, 12-30% of the M atoms can be substituted by Zn, which gradually occupies the center of the empty cubes. In all ternary compounds, smaller/less electronegative Zn/Cd atoms occupy the disordered tetrahedra explaining the lack of the YCd{sub 6}-type for pure mercurides. Along the section SrCd{sub 6}-SrHg{sub 6}, the ordered Eu{sub 4}Cd{sub 25}-type is formed (Sr{sub 4}Cd{sub 16.1}Hg{sub 8.9}: cF1392, Fd anti 3, a=3191.93(5) pm, R1=0.0404). Besides, two new complex cubic Ca phases appear at increased Zn proportion: Ca{sub 2}Zn{sub 5.1}Cd{sub 5.8}, which exhibits a nearly complete site preference of Zn and Cd, crystallizes in the rare cubic Mg{sub 2}Zn{sub 11}-type structure (cP39-δ, Pm anti 3, a=918.1(1) pm, R1=0.0349). In the Ca-Hg system, an increased Zn proportion yielded the new compound CaZn{sub 1.31}Hg{sub 3.69} (cF480, F anti 43m, a=2145.43(9) pm, R1=0.0572), with a complex cubic structure closely related to Ba{sub 20}Hg{sub 103}. All structures, which are commonly described using nested polyhedra around high-symmetric sites, are alternatively described in accordance with the calculated electron densities and charge distribution: building blocks are face-sharing [M{sub 4}] tetrahedra (star polyhedra such as TS, IS, OS), each with a cage-critical point in its center, and [M{sub 8}] cubes (deformed TS), which are either empty, distorted or filled. The M element distribution in the anion is determined by size criteria and the difference in electronegativity, which induces a preferred formation of heteroatomic polar bonds.

  5. Nb2OsB2, with a new twofold superstructure of the U3Si2 type: Synthesis, crystal chemistry and chemical bonding

    International Nuclear Information System (INIS)

    Mbarki, Mohammed; Touzani, Rachid St.; Fokwa, Boniface P.T.

    2013-01-01

    The new ternary metal-rich boride, Nb 2 OsB 2 , was synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. The compound was characterized from single-crystal X-ray data and EDX measurements. It crystallizes as a new superstructure (space group P4/mnc, no. 128) of the tetragonal U 3 Si 2 -structure type with lattice parameters a=5.922(1) Å and c=6.879(2) Å. All of the B atoms are involved in B 2 dumbbells with B–B distances of 1.89(4) Å. Structure relaxation using VASP (Vienna ab intio Simulation Package) has confirmed the space group and the lattice parameters. According to electronic structure calculations (TB–LMTO–ASA), the homoatomic B–B interactions are optimized and very strong, but relatively strong heteroatomic Os–B, Nb–B and Nb–Os bonds are also found: These interactions, which together build a three-dimensional network, are mainly responsible for the structural stability of this new phase. The density of state at the Fermi level predicts metallic behavior, as expected, from this metal-rich boride. - Graphical abstract: Nb 2 OsB 2 is, to the best of our knowledge, the first fully characterized phase in the ternary Nb–Os–B system. It crystallizes (space group P4/mnc, 128) with a new twofold superstructure of the U 3 Si 2 structure type (space group P4/mbm, 127), and is therefore the first boride in this structure family crystallizing with a superstructure of the U 3 Si 2 structure type. We show that the distortions leading to this superstructure occurs mainly in the Nb-layer, which tries to accommodate the large osmium atoms. The consequence of this puckering is the building osmium dumbbells instead of chains along [001]. - Highlights: • First compound in the Nb–Os–B system. • New twofold superstructure of U 3 Si 2 structure type. • Puckering of Nb-layer responsible for superstructure occurrence. • Chemical bonding studied by density functional theory

  6. New insights into the crystal chemistry of agardite-(Ce): refinement of the crystal structure, hydrogen bonding, and epitaxial intergrowths with the Sb-analogue of auriacusite

    Science.gov (United States)

    Aksenov, Sergey M.; Chukanov, Nikita V.; Göttlicher, Jörg; Möckel, Steffen; Varlamov, Dmitriy; Van, Konstantin V.; Rastsvetaeva, Ramiza K.

    2018-01-01

    Agardite-(Ce) from Clara Mine, Schwarzwald, Germany, has been investigated by means of electron microprobe analysis, single-crystal X-ray analysis, XANES spectroscopy and IR spectroscopy. Hexagonal unit-cell parameters are: a = 13.598(6), c = 5.954(3) Å; V = 953.5(2) Å3; space group P63/ m. The structure has been solved and refined to final R 1 = 3.87%, w R 2 = 5.02 for 786 I > 3 σ( I). Hydrogen atoms have been localized. The crystal-chemical formula is ( Z = 2): A(1)(Ce0.82Ca0.14Sr0.04)Σ1.00 A(2)(Ca0.03Ce0.02)Σ0.05 [Cu5.75(Fe3+, Mn)0.20]Σ5.95 [ T(1)(AsO4) 2.96 T(2) (SbO4)0.04)]Σ3.00 (OH)5.96O0.04·3H2O. Hydrogen bonding in agardite-series minerals has been characterized for the first time. IR spectra of agardite-(Ce) and agardite-(Nd) from Lavrion used for comparison, as well as structural data indicate the presence of isolated H+ cations that do not form strong covalent bonds with coordinating O atoms. Agardite-(Ce) from Clara Mine forms epitaxial growths with the Sb-analogue of auriacusite. The latter mineral was characterized by EDS analyses; its typical empirical formulae are {Ca}_{0.0 6} {Ce}_{0.0 4} {Fe}^{ 3+ }{}_{ 1.0 6} {Cu}_{0. 8 9}[(SbO4)0.58(AsO4)0.38(SiO4)0.04]Σ1.00(O,OH) and {Ca}_{0.0 7 5} {Ce}_{0.0 4} {Fe}^{ 3+ }{}_{0. 9 3} {Cu}_{0. 9 7}[(SbO4)0.59(AsO4)0.35(SiO4)0.06]Σ1.00(O,OH). The formation of uniaxial growths of the Sb-analogue of auriacusite and agardite-(Ce) is caused by the close values of their c parameters (for auriacusite s.s. c = 5.9501(5) Å). Three-valence state of iron and five-valence of antimony in both minerals has been validated by means of Fe K- and Sb L 2,3-edge XANES spectroscopy.

  7. Investigation of glutathione-derived electrostatic and hydrogen-bonding interactions and their role in defining Grx5 [2Fe-2S] cluster optical spectra and transfer chemistry.

    Science.gov (United States)

    Sen, Sambuddha; Bonfio, Claudia; Mansy, Sheref S; Cowan, J A

    2018-03-01

    Human glutaredoxin 5 (Grx5) is one of the core components of the Isc (iron-sulfur cluster) assembly and trafficking machinery, and serves as an intermediary cluster carrier, putatively delivering cluster from the Isu scaffold protein to target proteins. The tripeptide glutathione is intimately involved in this role, providing cysteinyl coordination to the iron center of the Grx5-bound [2Fe-2S] cluster. Grx5 has a well-defined glutathione-binding pocket with protein amino acid residues providing many ionic and hydrogen binding contacts to the bound glutathione. In this report, we investigated the importance of these interactions in cluster chirality and exchange reactivity by systematically perturbing the crucial contacts by use of natural and non-natural amino acid substitutions to disrupt the binding contacts from both the protein and glutathione. Native Grx5 could be reconstituted with all of the glutathione analogs used, as well as other thiol ligands, such as DTT or L-cysteine, by in vitro chemical reconstitution, and the holo proteins were found to transfer [2Fe-2S] cluster to apo ferredoxin 1 at comparable rates. However, the circular dichroism spectra of these derivatives displayed prominent differences that reflect perturbations in local cluster chirality. These studies provided a detailed molecular understanding of glutathione-protein interactions in holo Grx5 that define both cluster spectroscopy and exchange chemistry.

  8. Chemistry of oxovanadium(IV) bound to tetradentate ONNO donors; influence of axial coordination on the V-Osub(1) bond

    International Nuclear Information System (INIS)

    Maity, A.; Ghosh, S.

    1992-01-01

    Chelating behaviour of some tetradentate ONNO donors from q-aminobenzoylhydrazide and some diketones towards oxo-vanadium(IV) ion is reported. The donors react with oxometal cation depending on the pH of the reaction medium. The product containing the neutral keto and the binegative enol form of the donor have the formulae [Vo(H 2 L)(SO 4 )](at pH 3.0)(1) and [VO(L)(H 2 O)] (at pH 6.0) (2) respectively [H 2 L=(2-NH 2 )C 6 H 4 CONH: C(R).(CH 2 ) m C(R) : NNH CO.C 6 H 4 (2-NH 2 ); H 2 L=H 2 DA(R=CH 3 , m=0), H 2 BA(R=C 6 H 5 , m=0), H 2 AA(R=CH 3 , m=2)]. Both (1) and (2) react with a neutral monodentate donor B(B=pyridine, aniline etc.) yielding mixed-ligand complexes [VO(L)(B)]. Influence of the axial coordination on the V-Osub((1)) bond is discussed and a monomeric distorted octahedral donor environment for the oxovanadium(IV) ion has been suggested. (author). 2 refs., 2 tabs., 3 figs

  9. Nb2OsB2, with a new twofold superstructure of the U3Si2 type: Synthesis, crystal chemistry and chemical bonding

    Science.gov (United States)

    Mbarki, Mohammed; Touzani, Rachid St.; Fokwa, Boniface P. T.

    2013-07-01

    The new ternary metal-rich boride, Nb2OsB2, was synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. The compound was characterized from single-crystal X-ray data and EDX measurements. It crystallizes as a new superstructure (space group P4/mnc, no. 128) of the tetragonal U3Si2-structure type with lattice parameters a=5.922(1) Å and c=6.879(2) Å. All of the B atoms are involved in B2 dumbbells with B-B distances of 1.89(4) Å. Structure relaxation using VASP (Vienna ab intio Simulation Package) has confirmed the space group and the lattice parameters. According to electronic structure calculations (TB-LMTO-ASA), the homoatomic B-B interactions are optimized and very strong, but relatively strong heteroatomic Os-B, Nb-B and Nb-Os bonds are also found: These interactions, which together build a three-dimensional network, are mainly responsible for the structural stability of this new phase. The density of state at the Fermi level predicts metallic behavior, as expected, from this metal-rich boride.

  10. 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

  11. 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…

  12. DOE fundamentals handbook: Chemistry

    International Nuclear Information System (INIS)

    1993-01-01

    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

  13. 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)....

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

    International Nuclear Information System (INIS)

    Gaume, R.

    2002-11-01

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

  15. Selected Contributions of the 4th European Meeting on Solar Chemistry and Photocatalysis. Environmental Applications (SPEA 4)

    International Nuclear Information System (INIS)

    Malato Rodriguez, S.; Gernjak, W.; Pereze Pena, J.; Dona Rodriguez, J.M.

    2007-01-01

    In developed countries, the importance of water as a resource and problems derived from its scarcity has led to growing social and legislative demands. As a consequence, in the last 30 years, new fields of research have opened in a search for more efficient water treatment methods. This is the case of the advanced oxidation techniques (AOTs) and their application to nonbiodegradable contaminants, which can otherwise be removed from water, but not eliminated. Fast development of research in this field has encouraged chemists, chemical engineers and related professionals to meet and debate their findings and plan new strategies for the future, working toward evermore efficient methods of wastewater treatment wherever needed. The same can be said of gaseous effluents, as emission limits for organic air pollution become stricter. Volatile organic compounds (VOCs) pose an environmental and health threat, which can be treated by adsorption, incineration, condensation, etc., or be completely destroyed by chemical methods, such as the very promising gas-phase photocatalytic air pollution treatment. The SPEA Meetings have been held against this background, particularly this fourth one, where scientists assembled to present and debate their latest achievements in low-cost treatment technologies for wastewater, gaseous effluents and polluted soils. This Special Issue of Catalysis Today was compiled from the scientific reports generated by the congress, and includes a selection of some of the most interesting work presented at the meeting. The 34-member Scientific Committee were from 11 different countries (Argentina, Chile, Finland, France, Germany, Greece, Italy, Slovakia, Spain, Switzerland, and the USA). One hundred and thirty-five delegates from 22 different countries attended the congress (representing 368 authors). One hundred and thirty-eight communications were presented, 45 oral presentations and 93 posters. Three plenary lectures, one round table and two poster

  16. 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.

  17. Transuranic Computational Chemistry.

    Science.gov (United States)

    Kaltsoyannis, Nikolas

    2018-02-26

    Recent developments in the chemistry of the transuranic elements are surveyed, with particular emphasis on computational contributions. Examples are drawn from molecular coordination and organometallic chemistry, and from the study of extended solid systems. The role of the metal valence orbitals in covalent bonding is a particular focus, especially the consequences of the stabilization of the 5f orbitals as the actinide series is traversed. The fledgling chemistry of transuranic elements in the +II oxidation state is highlighted. Throughout, the symbiotic interplay of experimental and computational studies is emphasized; the extraordinary challenges of experimental transuranic chemistry afford computational chemistry a particularly valuable role at the frontier of the periodic table. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Determination of validity and reliability of performance assessments tasks developed for selected topics in high school chemistry

    Science.gov (United States)

    Zichittella, Gail Eberhardt

    The primary purpose of this study was to validate performance assessments, which can be used as teaching and assessment instruments in high school science classrooms. This study evaluated the classroom usability of these performance instruments and establishes the interrater reliability of the scoring rubrics when used by classroom teachers. The assessment instruments were designed to represent two levels of scientific inquiry. The high level of inquiry tasks are relatively unstructured in terms of student directions; the low inquiry tasks provided more structure for the student. The tasks cover two content topics studied in chemistry (scientific observation and density). Students from a variety of Western New York school districts who were enrolled in chemistry classes and other science courses were involved in completion of the tasks at the two levels of inquiry. The chemistry students completed the NYS Regents Examination in Chemistry. Their classroom teachers were interviewed and completed a questionnaire to aid in the establishment their epistemological view on the inclusion of inquiry based learning in the science classroom. Data showed that the performance assessment tasks were reliable, valid and helpful for obtaining a more complete picture of the students' scientific understanding. The teacher participants reported no difficulty with the usability of the task in the high school chemistry setting. Collected data gave no evidence of gender bias with reference to the performance tasks or the NYS Regents Chemistry Examination. Additionally, it was shown that the instructors' classroom practices do have an effect upon the students' achievement on the performance tasks and the NYS Regents examination. Data also showed that achievement on the performance tasks was influenced by the number of years of science instruction students had received.

  19. Analysis of Halogen and Other σ-Hole Bonds in Crystals

    Directory of Open Access Journals (Sweden)

    Peter Politzer

    2018-01-01

    Full Text Available Schneider has observed that [1]: “ . . . the chemistry of the last century was largely the chemistry of covalent bonding, whereas that of the present century is more likely to be the chemistry of noncovalent binding.”[...

  20. Functionalized Cobalt Triarylcorrole Covalently Bonded with Graphene Oxide: A Selective Catalyst for the Two- or Four-Electron Reduction of Oxygen.

    Science.gov (United States)

    Tang, Jijun; Ou, Zhongping; Guo, Rui; Fang, Yuanyuan; Huang, Dong; Zhang, Jing; Zhang, Jiaoxia; Guo, Song; McFarland, Frederick M; Kadish, Karl M

    2017-08-07

    A cobalt triphenylcorrole (CorCo) was covalently bonded to graphene oxide (GO), and the resulting product, represented as GO-CorCo, was characterized by UV-vis, FT-IR, and micro-Raman spectroscopy as well as by HRTEM, TGA, XRD, XPS, and AFM. The electrocatalytic activity of GO-CorCo toward the oxygen reduction reaction (ORR) was then examined in air-saturated 0.1 M KOH and 0.5 M H 2 SO 4 solutions by cyclic voltammetry and linear sweep voltammetry using a rotating disk electrode and/or a rotating ring-disk electrode. An overall 4-electron reduction of O 2 is obtained in alkaline media while under acidic conditions a 2-electron process is seen. The ORR results thus indicate that covalently bonded GO-CoCor can be used as a selective catalyst for either the 2- or 4-electron reduction of oxygen, the prevailing reaction depending upon the acidity of the solution.

  1. Applicability Of A Semi-Automated Clinical Chemistry Analyzer In Determining The Antioxidant Concentrations Of Selected Plants

    Directory of Open Access Journals (Sweden)

    Allan L. Hilario

    2017-07-01

    Full Text Available Plants are rich sources of antioxidants that are protective against diseases associated to oxidative stress. There is a need for high throughput screening method that should be useful in determining the antioxidant concentration in plants. Such screening method should significantly simplify and speed up most antioxidant assays. This paper aimed at comparing the applicability of a semi-automated clinical chemistry analyzer Pointe Scientific MI USA with the traditional standard curve method and using a Vis spectrophotometer in performing the DPPH assay for antioxidant screening. Samples of crude aqueous leaf extract of kulitis Amaranthus viridis Linn and chayote Sechium edule Linn were screened for the Total Antioxidant Concentration TAC using the two methods. Results presented in mean SD amp956gdl were compared using unpaired Students t-test P0.05. All runs were done in triplicates. The mean TAC of A. viridis was 646.0 45.5 amp956gdl using the clinical chemistry analyzer and 581.9 19.4 amp956gdl using the standard curve-spectrophotometer. On the other hand the mean TAC of S. edule was 660.2 35.9 amp956gdl using the semi-automated clinical chemistry analyzer and 672.3 20.9 amp956gdl using the spectrophotometer. No significant differences were observed between the readings of the two methods for A. viridis P0.05 and S. edible P0.05. This implies that the clinical chemistry analyzer can be an alternative method in conducting the DPPH assay to determine the TAC in plants. This study presented the applicability of a semi-automated clinical chemistry analyzer in performing the DPPH assay. Further validation can be conducted by performing other antioxidant assays using this equipment.

  2. Selectivity of primary events in the radiation chemistry of organic solids and polymers as revealed by model studies of ionized molecules

    International Nuclear Information System (INIS)

    Feldman, V.

    2006-01-01

    Selectivity of the primary chemical events induced by ionizing radiation in molecular systems is the key issue of basic radiation chemistry, which is crucially important for controlling the radiation sensitivity of various-type organic and polymeric materials and designing new effective approaches to the radiation modification. In the past decade we have demonstrated that many features of selective localization of the radiation-induced effects in molecular solids can be understood on the basis of model studies of the primary ionized molecules in rigid low-temperature matrices. This talk will outline the key results of these studies and possible implications for radiation chemistry of vatious systems. In particular, the following aspects will be considered: (1) Spectroscopic characteristics of ustable ionized molecules in low-temperature matrices and their correlations with the site-selective reactivity. (2) Experimental modeling of the effect of excess energy on the properties of primary ionized molecules in condensed phases. (3) Intramolecular long-range effects with particular impact on the properties of ionized bifunctional molecules of X-(CH 2 ) n -X and X-(CH 2 ) n -Y types. (4) Modeling of intermolecular long-range positive hole transfer between molecular traps with close ionization energy and manifestations of 'fine tuning' effects resulting from conformation variations and intermolecular interactions. Several illustrative examples of correlation between the properties of primary ionized molecules and selectivity of the radiation-chemical transformations in organic solids and macromolecules will be presented. Finally, the problem of prediction of the radiation-chemical behaviour of complex organic systems on the basis of limited spectroscopic information and quantum-chemical data obtained for model systems will be addressed. This work was supported by the Russian Foundation for Basic Research (Project No. 06-03-33104) and the Russian Academy of Sciences

  3. Fine chemistry

    International Nuclear Information System (INIS)

    Laszlo, P.

    1988-01-01

    The 1988 progress report of the Fine Chemistry laboratory (Polytechnic School, France) is presented. The research programs are centered on the renewal of the organic chemistry most important reactions and on the invention of new, highly efficient and highly selective reactions, by applying low cost reagents and solvents. An important research domain concerns the study and fabrication of new catalysts. They are obtained by means of the reactive sputtering of the metals and metal oxydes thin films. The Monte Carlo simulations of the long-range electrostatic interaction in a clay and the obtention of acrylamides from anhydrous or acrylic ester are summarized. Moreover, the results obtained in the field of catalysis are also given. The published papers and the congress communications are included [fr

  4. 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.

  5. Unravelling the secrets of Cs controlled secondary ion formation: Evidence of the dominance of site specific surface chemistry, alloying and ionic bonding

    Science.gov (United States)

    Wittmaack, Klaus

    2013-03-01

    implantation can be evaluated as a function of Cs coverage. The summarised results imply that secondary ions are commonly not formed by charge transfer between an escaping atom and the electronic system of the sample but are already emitted as ions. The probability of ion formation appears to be controlled by the local ionic character of the alkali-target atom bonds, i.e., by the difference in electronegativity between the involved elements as well as by the electron affinity and the ionisation potential of the departing atom. This idea is supported by the finding that Si- yields exhibit the same very strong dependence on Cs coverage as Si+ and O- yields on the oxygen fraction in oxygen loaded Si. Most challenging to theoreticians is the finding that the ionisation probability is independent of the emission velocity of sputtered ions. This phenomenon cannot be rationalised along established routes of thinking. Different concepts need to be explored. An old, somewhat exotic idea takes account of the heavy perturbation created for a very short period of time at the site of ion emission (dynamic randomisation). Molecular dynamics simulations are desirable to clarify the issue. Ultimately it may be possible to describe all phenomena of enhanced or suppressed secondary ion formation, produced either by surface loading with alkali atoms or by enforced surface oxidation, on the basis of a single universal model. There is plenty of room for exciting new studies.

  6. Effects of annealing temperatures on the morphological, mechanical, surface chemical bonding, and solar selectivity properties of sputtered TiAlSiN thin films

    International Nuclear Information System (INIS)

    Rahman, M. Mahbubur; Jiang, Zhong-Tao; Zhou, Zhi-feng; Xie, Zonghan; Yin, Chun Yang; Kabir, Humayun; Haque, Md. Mahbubul; Amri, Amun; Mondinos, Nicholas; Altarawneh, Mohammednoor

    2016-01-01

    Quaternary sputtered TiAlSiN coatings were investigated for their high temperature structural stability, surface morphology, mechanical behaviors, surface chemical bonding states, solar absorptance and thermal emittance for possible solar selective surface applications. The TiAlSiN films were synthesized, via unbalanced magnetron sputtered technology, on AISI M2 steel substrate and annealed at 500 °C - 800 °C temperature range. SEM micrographs show nanocomposite-like structure with amorphous grain boundaries. Nanoindentation analyses indicate a decrease of hardness, plastic deformation and constant yield strength for the coatings. XPS analysis show mixed Ti, Al and Si nitride and oxide as main coating components but at 800 °C the top layer of the coatings is clearly composed of only Ti and Al oxides. Synchrotron radiation XRD (SR-XRD) results indicate various Ti, Al and Si nitride and oxide phases, for the above annealing temperature range with a phase change occurring with the Fe component of the substrate. UV–Vis spectroscopy, FTIR spectroscopy studies determined a high solar selectivity, s of 24.6 for the sample annealed at 600 °C. Overall results show good structural and morphological stability of these coatings at temperatures up to 800 °C with a very good solar selectivity for real world applications. - Highlights: • TiAlSiN sputtered coatings were characterized for solar selective applications. • In situ synchrotron radiation XRD were studies show the occurrence of multiple stable phases. • A high selectivity of 24.63 has been achieved for the coatings annealed at 700 °C. • Existence of XRD phases were also confirmed by XPS measurements. • At high temperature annealing the mechanical properties of films were governed by the utmost surfaces of the films.

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

    International Nuclear Information System (INIS)

    Cronauer, D.C.

    2011-01-01

    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 expected for

  8. 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

  9. Applicability Of A Semi-Automated Clinical Chemistry Analyzer In Determining The Antioxidant Concentrations Of Selected Plants

    OpenAIRE

    Allan L. Hilario; Phylis C. Rio; Geraldine Susan C. Tengco; Danilo M. Menorca

    2017-01-01

    Plants are rich sources of antioxidants that are protective against diseases associated to oxidative stress. There is a need for high throughput screening method that should be useful in determining the antioxidant concentration in plants. Such screening method should significantly simplify and speed up most antioxidant assays. This paper aimed at comparing the applicability of a semi-automated clinical chemistry analyzer Pointe Scientific MI USA with the traditional standard curve method and...

  10. Stable and Inert Cobalt Catalysts for Highly Selective and Practical Hydrogenation of C≡N and C═O Bonds.

    Science.gov (United States)

    Chen, Feng; Topf, Christoph; Radnik, Jörg; Kreyenschulte, Carsten; Lund, Henrik; Schneider, Matthias; Surkus, Annette-Enrica; He, Lin; Junge, Kathrin; Beller, Matthias

    2016-07-20

    Novel heterogeneous cobalt-based catalysts have been prepared by pyrolysis of cobalt complexes with nitrogen ligands on different inorganic supports. The activity and selectivity of the resulting materials in the hydrogenation of nitriles and carbonyl compounds is strongly influenced by the modification of the support and the nitrogen-containing ligand. The optimal catalyst system ([Co(OAc)2/Phen@α-Al2O3]-800 = Cat. E) allows for efficient reduction of both aromatic and aliphatic nitriles including industrially relevant dinitriles to primary amines under mild conditions. The generality and practicability of this system is further demonstrated in the hydrogenation of diverse aliphatic, aromatic, and heterocyclic ketones as well as aldehydes, which are readily reduced to the corresponding alcohols.

  11. Influence of thermo-mechanical cycling on porcelain bonding to cobalt-chromium and titanium dental alloys fabricated by casting, milling, and selective laser melting.

    Science.gov (United States)

    Antanasova, Maja; Kocjan, Andraž; Kovač, Janez; Žužek, Borut; Jevnikar, Peter

    2018-04-01

    The aim has been to determine the effect of thermo-mechanical cycling on shear-bond-strength (SBS) of dental porcelain to Co-Cr and Ti-based alloys fabricated by casting, computer-numerical-controlled milling, and selective-laser-melting (SLM). Seven groups (n=22/group) of metal cylinders were fabricated by casting (Co-Cr and commercially pure-cpTi), milling (Co-Cr, cpTi, Ti-6Al-4V) or by SLM (Co-Cr and Ti-6Al-4V) and abraded with airborne-particles. The average surface roughness (R a ) was determined for each group. Dental porcelain was applied and each metal-ceramic combination was divided into two subgroups - stored in deionized water (24-h, 37°C), or subjected to both thermal (6000-cycles, between 5 and 60°C) and mechanical cycling (10 5 -cycles, 60N-load). SBS test-values and failure modes were recorded. Metal-ceramic interfaces were analyzed with a focused-ion-beam/scanning-electron-microscope (FIB/SEM) and energy-dispersive-spectroscopy (EDS). The elastic properties of the respective metal and ceramic materials were evaluated by instrumented-indentation-testing. The oxide thickness on intact Ti-based substrates was measured with Auger-electron-spectroscopy (AES). Data were analyzed using ANOVA, Tukey's HSD and t-tests (α=0.05). The SBS-means differed according to the metal-ceramic combination (p<0.0005) and to the fatigue conditions (p<0.0005). The failure modes and interface analyses suggest better porcelain adherence to Co-Cr than to Ti-based alloys. Values of R a were dependent on the metal substrate (p<0.0005). Ti-based substrates were not covered with thick oxide layers following digital fabrication. Ti-based alloys are more susceptible than Co-Cr to reduction of porcelain bond strength following thermo-mechanical cycling. The porcelain bond strength to Ti-based alloys is affected by the applied metal processing technology. Copyright © 2017 Japan Prosthodontic Society. Published by Elsevier Ltd. All rights reserved.

  12. 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.

  13. Teaching and Learning the Concept of Chemical Bonding

    Science.gov (United States)

    Levy Nahum, Tami; Mamlok-Naaman, Rachel; Hofstein, Avi; Taber, Keith S.

    2010-01-01

    Chemical bonding is one of the key and basic concepts in chemistry. The learning of many of the concepts taught in chemistry, in both secondary schools as well as in the colleges, is dependent upon understanding fundamental ideas related to chemical bonding. Nevertheless, the concept is perceived by teachers, as well as by learners, as difficult,…

  14. Chemistry of Technetium

    International Nuclear Information System (INIS)

    Omori, Takashi

    2001-01-01

    Since the late 1970's the coordination chemistry of technetium has been developed remarkably. The background of the development is obviously related to the use of technetium radiopharmaceuticals for diagnosis in nuclear medicine. Much attention has also been denoted to the chemical behavior of environmental 99 Tc released from reprocessing plants. This review covers the several aspects of technetium chemistry, including production of radioisotopes, analytical chemistry and coordination chemistry. In the analytical chemistry, separation of technetium, emphasizing chromatography and solvent extraction, is described together with spectrophotometric determination of technetium. In the coordination chemistry of technetium, a characteristic feature of the chemistry of Tc(V) complexes is referred from the view point of the formation of a wide variety of highly stable complexes containing the Tc=O or Tc≡N bond. Kinetic studies of the preparation of Tc(III) complexes using hexakis (thiourea) technetium(III) ion as a starting material are summarized, together with the base hydrolysis reactions of Tc(III), Tc(IV) and Tc(V) complexes. (author)

  15. Insights from Domain-Averaged Fermi Hole (DAFH) Analysis and Multicenter Bond Indices into the Nature of Be(0) Bonding.

    Czech Academy of Sciences Publication Activity Database

    Ponec, Robert; Cooper, D.L.

    2017-01-01

    Roč. 28, č. 4 (2017), s. 1033-1043 ISSN 1040-0400 Institutional support: RVO:67985858 Keywords : peculiarity of Be(0) bonding * DAFH analysis * multicenter bond indices Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.582, year: 2016

  16. Cyclodextrin chemistry

    International Nuclear Information System (INIS)

    Khan, M.Z.; Chuaqui, C.A.

    1990-05-01

    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

  17. 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

  18. 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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. 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

  20. 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...

  1. Scandium Terminal Imido Chemistry.

    Science.gov (United States)

    Lu, Erli; Chu, Jiaxiang; Chen, Yaofeng

    2018-02-20

    Research into transition metal complexes bearing multiply bonded main-group ligands has developed into a thriving and fruitful field over the past half century. These complexes, featuring terminal M═E/M≡E (M = transition metal; E = main-group element) multiple bonds, exhibit unique structural properties as well as rich reactivity, which render them attractive targets for inorganic/organometallic chemists as well as indispensable tools for organic/catalytic chemists. This fact has been highlighted by their widespread applications in organic synthesis, for example, as olefin metathesis catalysts. In the ongoing renaissance of transition metal-ligand multiple-bonding chemistry, there have been reports of M═E/M≡E interactions for the majority of the metallic elements of the periodic table, even some actinide metals. In stark contrast, the largest subgroup of the periodic table, rare-earth metals (Ln = Sc, Y, and lanthanides), have been excluded from this upsurge. Indeed, the synthesis of terminal Ln═E/Ln≡E multiple-bonding species lagged behind that of the transition metal and actinide congeners for decades. Although these species had been pursued since the discovery of a rare-earth metal bridging imide in 1991, such a terminal (nonpincer/bridging hapticities) Ln═E/Ln≡E bond species was not obtained until 2010. The scarcity is mainly attributed to the energy mismatch between the frontier orbitals of the metal and the ligand atoms. This renders the putative terminal Ln═E/Ln≡E bonds extremely reactive, thus resulting in the formation of aggregates and/or reaction with the ligand/environment, quenching the multiple-bond character. In 2010, the stalemate was broken by the isolation and structural characterization of the first rare-earth metal terminal imide-a scandium terminal imide-by our group. The double-bond character of the Sc═N bond was unequivocally confirmed by single-crystal X-ray diffraction. Theoretical investigations revealed the presence

  2. Chemical bond activation observed with an x-ray laser

    International Nuclear Information System (INIS)

    Beye, Martin; Öberg, Henrik; Xin, Hongliang

    2016-01-01

    The concept of bonding and anti-bonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Lastly, we apply time-resolved soft X-ray spectroscopy at a free-electron laser to directly observe the decreased bonding–anti-bonding splitting following bond-activation using an ultra short optical laser pulse.

  3. Molecular orbital studies of the bonding in heavy element organometallics

    International Nuclear Information System (INIS)

    Bursten, B.E.

    1990-01-01

    This progress report contains highlights of research projects in actinide chemistry. Projects covered are bonding in Np, Pu, and transplutonium organometallic compounds, applications of the discrete variational Xα method to actinide chemistry, ab initio calculations on actinide molecules, and experimental comparisons of organoactinide and organotransition metal chemistry. Also included is brief discussions on budgets, funding, invited papers and invited presentations. (JL)

  4. Covalent versus ionic bonding in alkalimetal fluoride oligomers

    NARCIS (Netherlands)

    Bickelhaupt, F.M.; Sola, M.; Fonseca Guerra, C.

    2007-01-01

    The most polar bond in chemistry is that between a fluorine and an alkalimetal atom. Inspired by our recent finding that other polar bonds (C - M and H - M) have important covalent contributions (i.e., stabilization due to bond overlap), we herein address the question if covalency is also essential

  5. Selective Inhibitors of Protozoan Protein N-myristoyltransferases as Starting Points for Tropical Disease Medicinal Chemistry Programs

    Science.gov (United States)

    Bell, Andrew S.; Mills, James E.; Williams, Gareth P.; Brannigan, James A.; Wilkinson, Anthony J.; Parkinson, Tanya; Leatherbarrow, Robin J.; Tate, Edward W.; Holder, Anthony A.; Smith, Deborah F.

    2012-01-01

    Inhibition of N-myristoyltransferase has been validated pre-clinically as a target for the treatment of fungal and trypanosome infections, using species-specific inhibitors. In order to identify inhibitors of protozoan NMTs, we chose to screen a diverse subset of the Pfizer corporate collection against Plasmodium falciparum and Leishmania donovani NMTs. Primary screening hits against either enzyme were tested for selectivity over both human NMT isoforms (Hs1 and Hs2) and for broad-spectrum anti-protozoan activity against the NMT from Trypanosoma brucei. Analysis of the screening results has shown that structure-activity relationships (SAR) for Leishmania NMT are divergent from all other NMTs tested, a finding not predicted by sequence similarity calculations, resulting in the identification of four novel series of Leishmania-selective NMT inhibitors. We found a strong overlap between the SARs for Plasmodium NMT and both human NMTs, suggesting that achieving an appropriate selectivity profile will be more challenging. However, we did discover two novel series with selectivity for Plasmodium NMT over the other NMT orthologues in this study, and an additional two structurally distinct series with selectivity over Leishmania NMT. We believe that release of results from this study into the public domain will accelerate the discovery of NMT inhibitors to treat malaria and leishmaniasis. Our screening initiative is another example of how a tripartite partnership involving pharmaceutical industries, academic institutions and governmental/non-governmental organisations such as Medical Research Council and Wellcome Trust can stimulate research for neglected diseases. PMID:22545171

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

    KAUST Repository

    Liu, Xiangqian; Jia, Jiaqi; Rueping, Magnus

    2017-01-01

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

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

    KAUST Repository

    Liu, Xiangqian

    2017-06-07

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

  8. Introductory quantum chemistry

    International Nuclear Information System (INIS)

    Chandra, A.K.

    1974-01-01

    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.)

  9. Halogen bonding in solution: thermodynamics and applications.

    Science.gov (United States)

    Beale, Thomas M; Chudzinski, Michael G; Sarwar, Mohammed G; Taylor, Mark S

    2013-02-21

    Halogen bonds are noncovalent interactions in which covalently bound halogens act as electrophilic species. The utility of halogen bonding for controlling self-assembly in the solid state is evident from a broad spectrum of applications in crystal engineering and materials science. Until recently, it has been less clear whether, and to what extent, halogen bonding could be employed to influence conformation, binding or reactivity in the solution phase. This tutorial review summarizes and interprets solution-phase thermodynamic data for halogen bonding interactions obtained over the past six decades and highlights emerging applications in molecular recognition, medicinal chemistry and catalysis.

  10. Bonds Boom.

    Science.gov (United States)

    Reynolds, Cathryn

    1989-01-01

    The combined effect of the "Serrano" decision and Proposition 13 left California school districts with aging, overcrowded facilities. Chico schools won a $18.5 million general obligation bond election for facilities construction. With $11 billion needed for new school construction, California will need to tap local sources. A sidebar…

  11. Biodesulfurization of Naphthothiophene and Benzothiophene through Selective Cleavage of Carbon-Sulfur Bonds by Rhodococcus sp. Strain WU-K2R

    Science.gov (United States)

    Kirimura, Kohtaro; Furuya, Toshiki; Sato, Rika; Ishii, Yoshitaka; Kino, Kuniki; Usami, Shoji

    2002-01-01

    Naphtho[2,1-b]thiophene (NTH) is an asymmetric structural isomer of dibenzothiophene (DBT), and in addition to DBT derivatives, NTH derivatives can also be detected in diesel oil following hydrodesulfurization treatment. Rhodococcus sp. strain WU-K2R was newly isolated from soil for its ability to grow in a medium with NTH as the sole source of sulfur, and growing cells of WU-K2R degraded 0.27 mM NTH within 7 days. WU-K2R could also grow in the medium with NTH sulfone, benzothiophene (BTH), 3-methyl-BTH, or 5-methyl-BTH as the sole source of sulfur but could not utilize DBT, DBT sulfone, or 4,6-dimethyl-DBT. On the other hand, WU-K2R did not utilize NTH or BTH as the sole source of carbon. By gas chromatography-mass spectrometry analysis, desulfurized NTH metabolites were identified as NTH sulfone, 2′-hydroxynaphthylethene, and naphtho[2,1-b]furan. Moreover, since desulfurized BTH metabolites were identified as BTH sulfone, benzo[c][1,2]oxathiin S-oxide, benzo[c][1,2]oxathiin S,S-dioxide, o-hydroxystyrene, 2-(2′-hydroxyphenyl)ethan-1-al, and benzofuran, it was concluded that WU-K2R desulfurized NTH and BTH through the sulfur-specific degradation pathways with the selective cleavage of carbon-sulfur bonds. Therefore, Rhodococcus sp. strain WU-K2R, which could preferentially desulfurize asymmetric heterocyclic sulfur compounds such as NTH and BTH through the sulfur-specific degradation pathways, is a unique desulfurizing biocatalyst showing properties different from those of DBT-desulfurizing bacteria. PMID:12147483

  12. Enhancing Academic Achievement and Retention in Senior Secondary School Chemistry through Discussion and Lecture Methods: A Case Study of Some Selected Secondary Schools in Gboko, Benue State, Nigeria

    Science.gov (United States)

    Omwirhiren, Efe M.

    2015-01-01

    The present study was initiated to determine how academic achievement and retention in chemistry is enhanced using the two instructional methods among SSII students and ascertained the differential performance of male and female students in chemistry with a view of improving student performance in chemistry. The study adopted a non-equivalent…

  13. Predictive Modeling in Actinide Chemistry and Catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Yang, Ping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

    2016-05-16

    These are slides from a presentation on predictive modeling in actinide chemistry and catalysis. The following topics are covered in these slides: Structures, bonding, and reactivity (bonding can be quantified by optical probes and theory, and electronic structures and reaction mechanisms of actinide complexes); Magnetic resonance properties (transition metal catalysts with multi-nuclear centers, and NMR/EPR parameters); Moving to more complex systems (surface chemistry of nanomaterials, and interactions of ligands with nanoparticles); Path forward and conclusions.

  14. 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)

  15. Chemistry Dashboard

    Science.gov (United States)

    The Chemistry Dashboard is part of a suite of dashboards developed by EPA to help evaluate the safety of chemicals. The Chemistry Dashboard provides access to a variety of information on over 700,000 chemicals currently in use.

  16. 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....

  17. Aquatic Chemistry

    International Nuclear Information System (INIS)

    Kim, Dong Yeun; Kim, Oh Sik; Kim, Chang Guk; Park, Cheong Gil; Lee, Gwi Hyeon; Lee, Cheol Hui

    1987-07-01

    This book deals aquatic chemistry, which treats water and environment, chemical kinetics, chemical balance like dynamical characteristic, and thermodynamics, acid-base chemistry such as summary, definition, kinetics, and PH design for mixture of acid-base chemistry, complex chemistry with definition, and kinetics, precipitation and dissolution on summary, kinetics of precipitation and dissolution, and balance design oxidation and resolution with summary, balance of oxidation and resolution.

  18. 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

  19. Comparative effects of oil palm and selective logging on erosion, river channels and water chemistry in Malaysian steeplands

    Science.gov (United States)

    Walsh, Rory; Nainar, Anand; Nurhidayu, Siti; Higton, Sam; Annammala, Kogilavani; Wall, Katy; Bidin, Kawi; Blake, William; Darling, Isabella

    2017-04-01

    Oil palm land-use has expanded greatly in recent decades in SE Asia and other parts of the wet tropics, including to steepland areas, where bench-terraced landscaping is involved. Retaining (and sometimes restoring) riparian forest strips and rainforest fragments on the steepest slopes have been adopted as elements of strategies designed to reduce adverse effects on runoff generation, erosion, downstream sedimentation, flooding and pollutional problems - as well as biodiversity and emissions. Results of catchment monitoring, soil erosion and sediment fingerprinting research in oil palm and selectively logged steeplands of eastern Sabah and Peninsular Malaysia are presented. The evidence indicates the greater scale and temporal persistence of effects that oil palm land-use (compared with selective logging) has had on suspended sediment dynamics, soil erosion, downstream sedimentation, channel geometry and dynamics and river pollution. The importance of (1) high densities of roads and tracks and (2) relatively impermeable bench-terraced terrain in enhancing runoff, sediment and nutrient outputs in storm events is stressed. Influences of oil palm management practices including riparian forest strips in increasing or reducing these effects are critically reviewed and ways of increasing the effectiveness of riparian forest strips are proposed. The design and rationale of current projects exploring and testing consequences of existing and proposed improved land management practices are briefly described. The key importance of involvement of people from the oil palm industry (including multinational companies, smallholders and their organizations) and Government bodies that are responsible for land-use policies and land management practices is stressed.

  20. Chemistry and Selective Tumor Cell Growth Inhibitory Activity of Polyketides from the South China Sea Sponge Plakortis sp.

    Science.gov (United States)

    Li, Jiao; Li, Cui; Riccio, Raffaele; Lauro, Gianluigi; Bifulco, Giuseppe; Li, Tie-Jun; Tang, Hua; Zhuang, Chun-Lin; Ma, Hao; Sun, Peng; Zhang, Wen

    2017-05-03

    Simplextone E ( 1 ), a new metabolite of polyketide origin, was isolated with eight known analogues ( 2 - 9 ) from the South China Sea sponge Plakortis sp. The relative configuration of the new compound was elucidated by a detailed analysis of the spectroscopic data and quantum mechanical calculation of NMR chemical shifts, aided by the newly reported DP4+ approach. Its absolute configuration was determined by the TDDFT/ECD calculation. Simplextone E ( 1 ) is proven to be one of the isomers of simplextone D. The absolute configuration at C-8 in alkyl chain of plakortone Q ( 2 ) was also assigned based on the NMR calculation. In the preliminary in vitro bioassay, compounds 6 and 7 showed a selective growth inhibitory activity against HCT-116 human colon cancer cells with IC 50 values of 8.3 ± 2.4 and 8.4 ± 2.3 μM, corresponding to that of the positive control, adriamycin (IC 50 4.1 μM). The two compounds also showed selective activities towards MCF-7 human breast cancer and K562 human erythroleukemia cells while compound 3 only displayed weak activity against K562 cells.

  1. Diffusion bonding

    International Nuclear Information System (INIS)

    Anderson, R.C.

    1976-01-01

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

  2. 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

    2015-11-07

    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.

  3. 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

  4. Highly selective SiO2 etching over Si3N4 using a cyclic process with BCl3 and fluorocarbon gas chemistries

    Science.gov (United States)

    Matsui, Miyako; Kuwahara, Kenichi

    2018-06-01

    A cyclic process for highly selective SiO2 etching with atomic-scale precision over Si3N4 was developed by using BCl3 and fluorocarbon gas chemistries. This process consists of two alternately performed steps: a deposition step using BCl3 mixed-gas plasma and an etching step using CF4/Ar mixed-gas plasma. The mechanism of the cyclic process was investigated by analyzing the surface chemistry at each step. BCl x layers formed on both SiO2 and Si3N4 surfaces in the deposition step. Early in the etching step, the deposited BCl x layers reacted with CF x radicals by forming CCl x and BF x . Then, fluorocarbon films were deposited on both surfaces in the etching step. We found that the BCl x layers formed in the deposition step enhanced the formation of the fluorocarbon films in the CF4 plasma etching step. In addition, because F radicals that radiated from the CF4 plasma reacted with B atoms while passing through the BCl x layers, the BCl x layers protected the Si3N4 surface from F-radical etching. The deposited layers, which contained the BCl x , CCl x , and CF x components, became thinner on SiO2 than on Si3N4, which promoted the ion-assisted etching of SiO2. This is because the BCl x component had a high reactivity with SiO2, and the CF x component was consumed by the etching reaction with SiO2.

  5. Forensic Chemistry

    Science.gov (United States)

    Bell, Suzanne

    2009-07-01

    Forensic chemistry is unique among chemical sciences in that its research, practice, and presentation must meet the needs of both the scientific and the legal communities. As such, forensic chemistry research is applied and derivative by nature and design, and it emphasizes metrology (the science of measurement) and validation. Forensic chemistry has moved away from its analytical roots and is incorporating a broader spectrum of chemical sciences. Existing forensic practices are being revisited as the purview of forensic chemistry extends outward from drug analysis and toxicology into such diverse areas as combustion chemistry, materials science, and pattern evidence.

  6. 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…

  7. The halogen bond: Nature and applications

    Science.gov (United States)

    Costa, Paulo J.

    2017-10-01

    The halogen bond, corresponding to an attractive interaction between an electrophilic region in a halogen (X) and a nucleophile (B) yielding a R-X⋯B contact, found applications in many fields such as supramolecular chemistry, crystal engineering, medicinal chemistry, and chemical biology. Their large range of applications also led to an increased interest in their study using computational methods aiming not only at understanding the phenomena at a fundamental level, but also to help in the interpretation of results and guide the experimental work. Herein, a succinct overview of the recent theoretical and experimental developments is given starting by discussing the nature of the halogen bond and the latest theoretical insights on this topic. Then, the effects of the surrounding environment on halogen bonds are presented followed by a presentation of the available method benchmarks. Finally, recent experimental applications where the contribution of computational chemistry was fundamental are discussed, thus highlighting the synergy between the lab and modeling techniques.

  8. Unicorns in the world of chemical bonding models.

    Science.gov (United States)

    Frenking, Gernot; Krapp, Andreas

    2007-01-15

    The appearance and the significance of heuristically developed bonding models are compared with the phenomenon of unicorns in mythical saga. It is argued that classical bonding models played an essential role for the development of the chemical science providing the language which is spoken in the territory of chemistry. The advent and the further development of quantum chemistry demands some restrictions and boundary conditions for classical chemical bonding models, which will continue to be integral parts of chemistry. Copyright (c) 2006 Wiley Periodicals, Inc.

  9. Herbal Therapies for Type 2 Diabetes Mellitus: Chemistry, Biology, and Potential Application of Selected Plants and Compounds

    Directory of Open Access Journals (Sweden)

    Cicero L. T. Chang

    2013-01-01

    Full Text Available Diabetes mellitus has been recognized since antiquity. It currently affects as many as 285 million people worldwide and results in heavy personal and national economic burdens. Considerable progress has been made in orthodox antidiabetic drugs. However, new remedies are still in great demand because of the limited efficacy and undesirable side effects of current orthodox drugs. Nature is an extraordinary source of antidiabetic medicines. To date, more than 1200 flowering plants have been claimed to have antidiabetic properties. Among them, one-third have been scientifically studied and documented in around 460 publications. In this review, we select and discuss blood glucose-lowering medicinal herbs that have the ability to modulate one or more of the pathways that regulate insulin resistance, β-cell function, GLP-1 homeostasis, and glucose (reabsorption. Emphasis is placed on phytochemistry, anti-diabetic bioactivities, and likely mechanism(s. Recent progress in the understanding of the biological actions, mechanisms, and therapeutic potential of compounds and extracts of plant origin in type 2 diabetes is summarized. This review provides a source of up-to-date information for further basic and clinical research into herbal therapy for type 2 diabetes. Emerging views on therapeutic strategies for type 2 diabetes are also discussed.

  10. 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

  11. A conformation-selective IR-UV study of the dipeptides Ac-Phe-Ser-NH2 and Ac-Phe-Cys-NH2: probing the SH···O and OH···O hydrogen bond interactions.

    Science.gov (United States)

    Yan, Bin; Jaeqx, Sander; van der Zande, Wim J; Rijs, Anouk M

    2014-06-14

    The conformational preferences of peptides are mainly controlled by the stabilizing effect of intramolecular interactions. In peptides with polar side chains, not only the backbone but also the side chain interactions determine the resulting conformations. In this paper, the conformational preferences of the capped dipeptides Ac-Phe-Ser-NH2 (FS) and Ac-Phe-Cys-NH2 (FC) are resolved under laser-desorbed jet cooling conditions using IR-UV ion dip spectroscopy and density functional theory (DFT) quantum chemistry calculations. As serine (Ser) and cysteine (Cys) only differ in an OH (Ser) or SH (Cys) moiety; this subtle alteration allows us to study the effect of the difference in hydrogen bonding for an OH and SH group in detail, and its effect on the secondary structure. IR absorption spectra are recorded in the NH stretching region (3200-3600 cm(-1)). In combination with quantum chemical calculations the spectra provide a direct view of intramolecular interactions. Here, we show that both FS as FC share a singly γ-folded backbone conformation as the most stable conformer. The hydrogen bond strength of OH···O (FS) is stronger than that of SH···O (FC), resulting in a more compact gamma turn structure. A second conformer is found for FC, showing a β turn interaction.

  12. 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.

  13. Anion-selective interaction and colorimeter by an optical metalloreceptor based on ruthenium(II) 2,2'-biimidazole: hydrogen bonding and proton transfer.

    Science.gov (United States)

    Cui, Ying; Mo, Hao-Jun; Chen, Jin-Can; Niu, Yan-Li; Zhong, Yong-Rui; Zheng, Kang-Cheng; Ye, Bao-Hui

    2007-08-06

    A new anion sensor [Ru(bpy)2(H2biim)](PF6)2 (1) (bpy = 2,2'-bipyridine and H2biim = 2,2'-biimidazole) has been developed, in which the Ru(II)-bpy moiety acts as a chromophore and the H2biim ligand as an anion receptor via hydrogen bonding. A systematic investigation shows that 1 is an eligible sensor for various anions. It donates protons for hydrogen bonding to Cl-, Br-, I-, NO3-, HSO4-, H2PO4-, and OAc- anions and further actualizes monoproton transfer to the OAc- anion, changing color from yellow to orange brown. The fluoride ion has a high affinity toward the N-H group of the H2biim ligand for proton transfer, rather than hydrogen bonding, because of the formation of the highly stable HF2- anion, resulting in stepwise deprotonation of the two N-H fragments. These processes are signaled by vivid color changes from yellow to orange brown and then to violet because of second-sphere donor-acceptor interactions between Ru(II)-H2biim and the anions. The significant color changes can be distinguished visually. The processes are not only determined by the basicity of anion but also by the strength of hydrogen bonding and the stability of the anion-receptor complexes. The design strategy and remarkable photophysical properties of sensor 1 help to extend the development of anion sensors.

  14. Oxidative addition of C--H bonds in organic molecules to transition metal centers

    International Nuclear Information System (INIS)

    Bergman, R.G.

    1989-04-01

    Alkanes are among the most chemically inert organic molecules. They are reactive toward a limited range of reagents, such as highly energetic free radicals and strongly electrophilic and oxidizing species. This low reactivity is a consequence of the C--H bond energies in most saturated hydrocarbons. These values range from 90 to 98 kcal/mole for primary and secondary C--H bonds; in methane, the main constituent of natural gas, the C--H bond energy is 104 kcal/mole. This makes methane one of the most common but least reactive organic molecules in nature. This report briefly discusses the search for metal complexes capable of undergoing the C--H oxidative addition process allowing alkane chemistry to be more selective than that available using free radical reagents. 14 refs

  15. 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

  16. Radiation chemistry

    Energy Technology Data Exchange (ETDEWEB)

    None

    1973-07-01

    Research progress is reported on radiation chemistry of heavy elements that includes the following topics: radiation chemistry of plutonium in nitric acid solutions (spectrophotometric analysis and gamma radiolysis of Pu(IV) and Pu(VI) in nitric acid solution); EPR studies of intermediates formed in radiolytic reactions with aqueous medium; two-phase radiolysis and its effect on the distribution coefficient of plutonium; and radiation chemistry of nitric acid. (DHM)

  17. 2012 Gordon Research Conference, Organometallic Chemistry, 8-13 2012

    Energy Technology Data Exchange (ETDEWEB)

    Hillhouse, Gregory [Univ. of Chicago, IL (United States)

    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.

  18. Technetium chemistry

    International Nuclear Information System (INIS)

    Burns, C.; Bryan, J.; Cotton, F.; Ott, K.; Kubas, G.; Haefner, S.; Barrera, J.; Hall, K.; Burrell, A.

    1996-01-01

    Technetium chemistry is a young and developing field. Despite the limited knowledge of its chemistry, technetium is the workhorse for nuclear medicine. Technetium is also a significant environmental concern because it is formed as a byproduct of nuclear weapons production and fission-power generators. Development of new technetium radio-pharmaceuticals and effective environmental control depends strongly upon knowledge of basic technetium chemistry. The authors performed research into the basic coordination and organometallic chemistry of technetium and used this knowledge to address nuclear medicine and environmental applications. This is the final report of a three-year Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL)

  19. Chemistry Technology

    Data.gov (United States)

    Federal Laboratory Consortium — Chemistry technology experts at NCATS engage in a variety of innovative translational research activities, including:Design of bioactive small molecules.Development...

  20. 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

  1. Selected Contributions of the 6th European Meeting on Solar Chemistry and Photocatalysis: Environmental Applications (SPEA 6), 13th to 16th June 2010 Introduction

    Czech Academy of Sciences Publication Activity Database

    Klusoň, Petr; Krýsa, J.; Malato, S.; Oller, I.

    2011-01-01

    Roč. 161, č. 1 (2011), s. 2-2 ISSN 0920-5861 Grant - others:SMS(ES) CTQ2009-13459-C05-01 Institutional research plan: CEZ:AV0Z40720504 Keywords : solar light * environmental chemistry * photochemistry Subject RIV: CC - Organic Chemistry Impact factor: 3.407, year: 2011

  2. 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

    Energy Technology Data Exchange (ETDEWEB)

    Swain, Basudev, E-mail: swain@iae.re.kr [Institute for Advanced Engineering, Advanced Materials & Processing Center, Yongin, 449-863 (Korea, Republic of); Mishra, Chinmayee [Institute for Advanced Engineering, Advanced Materials & Processing Center, Yongin, 449-863 (Korea, Republic of); Hong, Hyun Seon [Sungshin University, Dept. of Interdisciplinary ECO Science, Seoul, 142-732 (Korea, Republic of); Cho, Sung-Soo [Institute for Advanced Engineering, Advanced Materials & Processing Center, Yongin, 449-863 (Korea, Republic of)

    2016-05-15

    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 6.11 kg/m{sup 3} of copper and 1.35 kg/m{sup 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 100–500 nm 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. - Highlights: • From the Indium-Tin-Oxide etching

  3. 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

    International Nuclear Information System (INIS)

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

    2016-01-01

    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 6.11 kg/m 3 of copper and 1.35 kg/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 100–500 nm 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. - Highlights: • From the Indium-Tin-Oxide etching wastewater

  4. Migration chemistry

    International Nuclear Information System (INIS)

    Carlsen, L.

    1992-05-01

    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 K D 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.)

  5. Alkali-bonded ceramics with hierarchical tailored porosity

    Czech Academy of Sciences Publication Activity Database

    Landi, E.; Medri, V.; Papa, E.; Dědeček, Jiří; Klein, Petr; Benito, P.; Vaccari, A.

    2013-01-01

    Roč. 73, SI (2013), s. 56-64 ISSN 0169-1317 Institutional support: RVO:61388955 Keywords : alkali-bonded ceramics * metalcaolin * geopolymerization parameters Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.703, year: 2013

  6. Zn Coordination Chemistry:  Development of Benchmark Suites for Geometries, Dipole Moments, and Bond Dissociation Energies and Their Use To Test and Validate Density Functionals and Molecular Orbital Theory.

    Science.gov (United States)

    Amin, Elizabeth A; Truhlar, Donald G

    2008-01-01

    We present nonrelativistic and relativistic benchmark databases (obtained by coupled cluster calculations) of 10 Zn-ligand bond distances, 8 dipole moments, and 12 bond dissociation energies in Zn coordination compounds with O, S, NH3, H2O, OH, SCH3, and H ligands. These are used to test the predictions of 39 density functionals, Hartree-Fock theory, and seven more approximate molecular orbital theories. In the nonrelativisitic case, the M05-2X, B97-2, and mPW1PW functionals emerge as the most accurate ones for this test data, with unitless balanced mean unsigned errors (BMUEs) of 0.33, 0.38, and 0.43, respectively. The best local functionals (i.e., functionals with no Hartree-Fock exchange) are M06-L and τ-HCTH with BMUEs of 0.54 and 0.60, respectively. The popular B3LYP functional has a BMUE of 0.51, only slightly better than the value of 0.54 for the best local functional, which is less expensive. Hartree-Fock theory itself has a BMUE of 1.22. The M05-2X functional has a mean unsigned error of 0.008 Å for bond lengths, 0.19 D for dipole moments, and 4.30 kcal/mol for bond energies. The X3LYP functional has a smaller mean unsigned error (0.007 Å) for bond lengths but has mean unsigned errors of 0.43 D for dipole moments and 5.6 kcal/mol for bond energies. The M06-2X functional has a smaller mean unsigned error (3.3 kcal/mol) for bond energies but has mean unsigned errors of 0.017 Å for bond lengths and 0.37 D for dipole moments. The best of the semiempirical molecular orbital theories are PM3 and PM6, with BMUEs of 1.96 and 2.02, respectively. The ten most accurate functionals from the nonrelativistic benchmark analysis are then tested in relativistic calculations against new benchmarks obtained with coupled-cluster calculations and a relativistic effective core potential, resulting in M05-2X (BMUE = 0.895), PW6B95 (BMUE = 0.90), and B97-2 (BMUE = 0.93) as the top three functionals. We find significant relativistic effects (∼0.01 Å in bond lengths, ∼0

  7. 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.

  8. Uranium chemistry research unit

    International Nuclear Information System (INIS)

    Anon.

    1978-01-01

    The initial field of research of this Unit, established in 1973, was the basic co-ordination chemistry of uranium, thorium, copper, cobalt and nickel. Subsequently the interest of the Unit extended to extractive metallurgy relating to these metals. Under the term 'co-ordination chemistry' is understood the interaction of the central transition metal ion with surrounding atoms in its immediate vicinity (within bonding distance) and the influence they have on each other - for example, structural studies for determining the number and arrangement of co-ordinated atoms and spectrophotometric studies to establish how the f electron energy levels of uranium are influenced by the environment. New types of uranium compounds have been synthesized and studied, and the behaviour of uranium ions in non-aqueous systems has also received attention. This work can be applied to the development and study of extractants and new extractive processes for uranium

  9. Ab initio quantum chemistry for combustion

    International Nuclear Information System (INIS)

    Page, M.; Lengsfield, B.H.

    1991-01-01

    Advances in theoretical and computational methods, coupled with the rapid development of powerful and inexpensive computers, fuel the current rapid development in computational quantum chemistry (QC). Nowhere is this more evident than in the areas of QC most relevant to combustion: the description of bond breaking and rate phenomena. although the development of faster computers with larger memories has had a major impact on the scope of problems that can be addressed with QC, the development of new theoretical techniques and capabilities is responsible for adding new dimensions in QC and has paved the way for the unification of QC electronic structure calculations with statistical and dynamical models of chemical reactions. These advances will be stressed in this chapter. This paper describes past accomplishments selectively to set the stage for discussion of ideas or techniques that we believe will have significant impact on combustion research. Thus, the focus of the chapter is as much on the future as it is on the past

  10. Current organic chemistry

    National Research Council Canada - National Science Library

    1997-01-01

    Provides in depth reviews on current progress in the fields of asymmetric synthesis, organometallic chemistry, bioorganic chemistry, heterocyclic chemistry, natural product chemistry, and analytical...

  11. Quantum mechanical facets of chemical bonds

    International Nuclear Information System (INIS)

    Daudel, R.

    1976-01-01

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

  12. Isolation and characterization of a uranium(VI)-nitride triple bond

    Science.gov (United States)

    King, David M.; Tuna, Floriana; McInnes, Eric J. L.; McMaster, Jonathan; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.

    2013-06-01

    The nature and extent of covalency in uranium bonding is still unclear compared with that of transition metals, and there is great interest in studying uranium-ligand multiple bonds. Although U=O and U=NR double bonds (where R is an alkyl group) are well-known analogues to transition-metal oxo and imido complexes, the uranium(VI)-nitride triple bond has long remained a synthetic target in actinide chemistry. Here, we report the preparation of a uranium(VI)-nitride triple bond. We highlight the importance of (1) ancillary ligand design, (2) employing mild redox reactions instead of harsh photochemical methods that decompose transiently formed uranium(VI) nitrides, (3) an electrostatically stabilizing sodium ion during nitride installation, (4) selecting the right sodium sequestering reagent, (5) inner versus outer sphere oxidation and (6) stability with respect to the uranium oxidation state. Computational analyses suggest covalent contributions to U≡N triple bonds that are surprisingly comparable to those of their group 6 transition-metal nitride counterparts.

  13. 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…

  14. Nuclear chemistry

    International Nuclear Information System (INIS)

    Vertes, A.; Kiss, I.

    1987-01-01

    This book is an introduction to the application of nuclear science in modern chemistry. The first group of chapters discuss the basic phenomena and concepts of nuclear physics with emphasis on their relation to chemical problems, including the main properties and the composition of atomic nuclei, nuclear reactions, radioactive decay and interactions of radiation with matter. These chapters provide the basis for understanding the following chapters which encompass the wide scope of nuclear chemistry. The methods of the investigation of chemical structure based on the interaction of nuclear radiation with matter including positronium chemistry and other exotic atoms is elaborated in particular detail. Separate chapters are devoted to the use of radioactive tracers, the chemical consequences of nuclear processes (i.e. hot atom chemistry), radiation chemistry, isotope effects and their applications, and the operation of nuclear reactors

  15. Nuclear chemistry

    International Nuclear Information System (INIS)

    Vertes, A.; Kiss, I.

    1987-01-01

    This book is an introduction to the application of nuclear science in modern chemistry. The first group of chapters discuss the basic phenomena and concepts of nuclear physics with emphasis on their relation to chemical problems, including the main properties and the composition of atomic nuclei, nuclear reactions, radioactive decay and interactions of radiation with matter. These chapters provide the basis for understanding the following chapters which encompass the wide scope of nuclear chemistry. The methods of the investigation of chemical structure based on the interaction of nuclear radiation with matter including positronium chemistry and other exotic atoms is elaborated in particular detail. Separate chapters are devoted to the use of radioactive tracers, the chemical consequences of nuclear processes (i.e. hot atom chemistry), radiation chemistry, isotope effects and their applications, and the operation of nuclear reactors. (Auth.)

  16. Diffusion bonding in compact heat exchangers

    International Nuclear Information System (INIS)

    Southall, David

    2009-01-01

    Heatric's diffusion bonding process is a solid-state joining technology that produces strong, compact, all-metal heat exchanger cores. Diffusion bonding allows for a large quantity of joints to be made in geometries that would normally be inaccessible for conventional welding techniques. Since Heatric's diffusion bonding process uses no interlayer or braze alloy, the resulting heat exchanger core has consistent chemistry throughout and, under carefully controlled conditions, a return to parent metal strength can be reached. This paper will provide an overview of the diffusion bonding process and its origins, and also its application to compact heat exchanger construction. The paper will then discuss recent work that has been done to compare mechanical properties of Heatric's diffusion bonded material with material that has been conventionally welded, as well as with material tested in the as-received condition. (author)

  17. Anisotropic surface chemistry properties and adsorption behavior of silicate mineral crystals.

    Science.gov (United States)

    Xu, Longhua; Tian, Jia; Wu, Houqin; Fang, Shuai; Lu, Zhongyuan; Ma, Caifeng; Sun, Wei; Hu, Yuehua

    2018-03-07

    Anisotropic surface properties of minerals play an important role in a variety of fields. With a focus on the two most intensively investigated silicate minerals (i.e., phyllosilicate minerals and pegmatite aluminosilicate minerals), this review highlights the research on their anisotropic surface properties based on their crystal structures. Four surface features comprise the anisotropic surface chemistry of minerals: broken bonds, energy, wettability, and charge. Analysis of surface broken bond and energy anisotropy helps to explain the cleavage and growth properties of mineral crystals, and understanding surface wettability and charge anisotropy is critical to the analysis of minerals' solution behavior, such as their flotation performance and rheological properties. In a specific reaction, the anisotropic surface properties of minerals are reflected in the adsorption strengths of reagents on different mineral surfaces. Combined with the knowledge of mineral crushing and grinding, a thorough understanding of the anisotropic surface chemistry properties and the anisotropic adsorption behavior of minerals will lead to the development of effective relational models comprising their crystal structure, surface chemistry properties, and targeted reagent adsorption. Overall, such a comprehensive approach is expected to firmly establish the connection between selective cleavage of mineral crystals for desired surfaces and designing novel reagents selectively adsorbed on the mineral surfaces. As tools to characterize the anisotropic surface chemistry properties of minerals, DLVO theory, atomic force microscopy (AFM), and molecular dynamics (MD) simulations are also reviewed. Copyright © 2017 Elsevier B.V. All rights reserved.

  18. Improper, Blue-Shifting Hydrogen Bond

    Czech Academy of Sciences Publication Activity Database

    Hobza, Pavel; Havlas, Zdeněk

    2002-01-01

    Roč. 108, - (2002), s. 325-334 ISSN 1432-881X R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4055905; CEZ:AV0Z4040901 Keywords : improper, blue-shifting hydrogen bond * properties * nature Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.421, year: 2002

  19. News: Green Chemistry & Technology

    Science.gov (United States)

    A series of 21 articles focused on different features of green chemistry in a recent issue of Chemical Reviews. Topics extended over a wide range to include the design of sustainable synthetic processes to biocatalysis. A selection of perspectives follows as part of this colu

  20. 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,

  1. Bond strength of masonry

    NARCIS (Netherlands)

    Pluijm, van der R.; Vermeltfoort, A.Th.

    1992-01-01

    Bond strength is not a well defined property of masonry. Normally three types of bond strength can be distinguished: - tensile bond strength, - shear (and torsional) bond strength, - flexural bond strength. In this contribution the behaviour and strength of masonry in deformation controlled uniaxial

  2. Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions

    Czech Academy of Sciences Publication Activity Database

    Grüner, Bohumír; Plešek, Jaromír; Báča, Jiří; Císařová, I.; Dozol, J. F.; Rouquette, H.; Vinas, C.; Selucký, P.; Rais, J.

    2002-01-01

    Roč. 26, č. 10 (2002), s. 1519-1527 ISSN 1144-0546 R&D Projects: GA ČR GA104/99/1096; GA ČR GA104/01/0142; GA ČR GA203/99/M037; GA MŠk LN00A028 Institutional research plan: CEZ:AV0Z4032918 Keywords : LIQUID-CHROMATOGRAPHIC SEPARATIONS * BORON-CLUSTER COMPOUNDS * CALIXARENES Subject RIV: CA - Inorganic Chemistry Impact factor: 2.060, year: 2002

  3. Evaluation of the corrosion, reactivity and chemistry control aspects for the selection of an alternative coolant in the secondary circuit of sodium fast reactors

    International Nuclear Information System (INIS)

    Brissonneau, L.; Simon, N.; Balbaud-Celerier, F.; Courouau, J.L.; Martinelli, L.; Grabon, V.; Capitaine, A.; Conocar, O.; Blat, M.

    2009-01-01

    Full text of publication follows: Sodium Fast Reactors are promising fourth generation reactors as they can contribute to reduce resource demand in uranium and considerably reduce waste level due to their fast spectrum. However, progress can be obtained for these reactors on the investment cost and on safety improvement. To achieve these goals, one of the innovative solutions consists in eliminating the reaction of sodium with water in the steam generators, by replacing the sodium in the secondary circuit by another coolant. A work group composed of experts from CEA, Areva NP and EdF was in charge to evaluate several alternative coolants as Heavy Liquid Metals (HLM), nitrate salts and hydroxide mixtures, through a multi-criteria analysis. Three important criteria for the selection of one coolant are its 'Interactions with the structures', and its 'chemistry control', and 'Reactivity with fluids' which are strongly correlated. The assessment, mainly based on the state-of-art from published literature on these points, is detailed in this paper. The mechanisms of corrosion of steels by the HLM depend on the oxygen content. For Pb-Bi, it has been modelled for oxidation and release domains. The corrosion of steels by nitrate salts presents similarity with the oxidation induced by HLM. The highly corrosive hydroxide mixture requires the use of nickel base alloys, for which oxidation and mass transfer are nevertheless significant. The HLM requires a fine regulation of oxygen content, through measurements and control systems, both to prevent lead oxide precipitation at high level and release corrosion at low level. Nitrate salts decompose into nitrites at sufficiently high temperature, which might induce pressure build-up in the circuit. The hydroxides must be kept under reducing atmosphere to lower the corrosion rate. Though these coolants are relatively inert to air and water, one of the main drawbacks of HLM and nitrate salts are their reactivity with sodium. Bismuth

  4. Advances in Solid-State Transformations of Coordination Bonds: From the Ball Mill to the Aging Chamber

    Directory of Open Access Journals (Sweden)

    Cristina Mottillo

    2017-01-01

    Full Text Available Controlling the formation of coordination bonds is pivotal to the development of a plethora of functional metal-organic materials, ranging from coordination polymers, metal-organic frameworks (MOFs to metallodrugs. The interest in and commercialization of such materials has created a need for more efficient, environmentally-friendly routes for making coordination bonds. Solid-state coordination chemistry is a versatile greener alternative to conventional synthesis, offering quantitative yields, enhanced stoichiometric and topological selectivity, access to a wider range of precursors, as well as to molecules and materials not readily accessible in solution or solvothermally. With a focus on mechanochemical, thermochemical and “accelerated aging” approaches to coordination polymers, including pharmaceutically-relevant materials and microporous MOFs, this review highlights the recent advances in solid-state coordination chemistry and techniques for understanding the underlying reaction mechanisms.

  5. Effects of ion concentration on the hydrogen bonded structure of ...

    Indian Academy of Sciences (India)

    WINTEC

    Effects of ion concentration on the hydrogen bonded structure of water in the vicinity of ions in aqueous NaCl solutions. A NAG. 1. , D CHAKRABORTY and A CHANDRA*. Department of Chemistry, Indian Institute of Technology, Kanpur 208 016. 1. Present address: Department of Chemistry and Chemical Engineering,.

  6. Defining the hydrogen bond: An account (IUPAC Technical Report)

    Czech Academy of Sciences Publication Activity Database

    Arunan, E.; Desiraju, G. R.; Klein, R. A.; Sadlej, J.; Scheiner, S.; Alkorta, I.; Clary, D. C.; Crabtree, R. H.; Dannenberg, J. J.; Hobza, Pavel; Kjaergaard, H. G.; Legon, A. C.; Mennucci, B.; Nesbitt, D. J.

    2011-01-01

    Roč. 83, č. 8 (2011), s. 1619-1636 ISSN 0033-4545 Institutional research plan: CEZ:AV0Z40550506 Keywords : bonding * electrostatic interactions * hydrogen bonding * molecular interactions Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.789, year: 2011

  7. Alpha-cyclodextrins reversibly capped with disulfide bonds

    Czech Academy of Sciences Publication Activity Database

    Kumprecht, Lukáš; Buděšínský, Miloš; Bouř, Petr; Kraus, Tomáš

    2010-01-01

    Roč. 34, č. 10 (2010), s. 2254-2260 ISSN 1144-0546 R&D Projects: GA AV ČR IAA400550810 Institutional research plan: CEZ:AV0Z40550506 Keywords : cyclodextrins * disulfide bond * dynamic covalent bond Subject RIV: CC - Organic Chemistry Impact factor: 2.631, year: 2010

  8. In vitro Comparative Evaluation of Tensile Bond Strength of 6(th), 7(th) and 8(th) Generation Dentin Bonding Agents.

    Science.gov (United States)

    Kamble, Suresh S; Kandasamy, Baburajan; Thillaigovindan, Ranjani; Goyal, Nitin Kumar; Talukdar, Pratim; Seal, Mukut

    2015-05-01

    Newer dentin bonding agents were developed to improve the quality of composite restoration and to reduce time consumption in its application. The aim of the present study was to evaluate tensile bond strength of 6(th), 7(th) and 8(th) generation bonding agents by in vitro method. Selected 60 permanent teeth were assigned into 20 in each group (Group I: 6(th) generation bonding agent-Adper SE plus 3M ESPE, Group II: 7(th) generation bonding agent-G-Bond GC Corp Japan and Group III: 8(th) generation dentin adhesives-FuturaBond, DC, Voco, Germany). With high-speed diamond disc, coronal dentin was exposed, and selected dentin bonding agents were applied, followed by composite restoration. All samples were saved in saline for 24 h and tensile bond strength testing was done using a universal testing machine. The obtained data were tabulated and statistically analyzed using ANOVA test. The tensile bond strength readings for 6(th) generation bonding agent was 32.2465, for 7(th) generation was 31.6734, and for 8(th)-generation dentine bonding agent was 34.74431. The highest tensile bond strength was seen in 8(th) generation bonding agent compared to 6(th) and 7(th) generation bonding agents. From the present study it can be conclude that 8(th) generation dentine adhesive (Futura DC, Voco, Germany) resulted in highest tensile bond strength compared to 6(th) (Adper SE plus, 3M ESPE) and 7(th) generation (G-Bond) dentin bonding agents.

  9. 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...

  10. Analytical chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Choi, Jae Seong

    1993-02-15

    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.

  11. Analytical chemistry

    International Nuclear Information System (INIS)

    Choi, Jae Seong

    1993-02-01

    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.

  12. Analytical chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Chae, Myeong Hu; Lee, Hu Jun; Kim, Ha Seok

    1989-02-15

    This book give explanations on analytical chemistry with ten chapters, which deal with development of analytical chemistry, the theory of error with definition and classification, sample and treatment gravimetry on general process of gravimetry in aqueous solution and non-aqueous solution, precipitation titration about precipitation reaction and types, complexometry with summary and complex compound, oxidation-reduction equilibrium on electrode potential and potentiometric titration, solvent extraction and chromatograph and experiment with basic operation for chemical experiment.

  13. Analytical chemistry

    International Nuclear Information System (INIS)

    Chae, Myeong Hu; Lee, Hu Jun; Kim, Ha Seok

    1989-02-01

    This book give explanations on analytical chemistry with ten chapters, which deal with development of analytical chemistry, the theory of error with definition and classification, sample and treatment gravimetry on general process of gravimetry in aqueous solution and non-aqueous solution, precipitation titration about precipitation reaction and types, complexometry with summary and complex compound, oxidation-reduction equilibrium on electrode potential and potentiometric titration, solvent extraction and chromatograph and experiment with basic operation for chemical experiment.

  14. 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.

  15. Representational Classroom Practices that Contribute to Students' Conceptual and Representational Understanding of Chemical Bonding

    Science.gov (United States)

    Hilton, Annette; Nichols, Kim

    2011-01-01

    Understanding bonding is fundamental to success in chemistry. A number of alternative conceptions related to chemical bonding have been reported in the literature. Research suggests that many alternative conceptions held by chemistry students result from previous teaching; if teachers are explicit in the use of representations and explain their…

  16. A Cost-Effective Physical Modeling Exercise to Develop Students' Understanding of Covalent Bonding

    Science.gov (United States)

    Turner, Kristy L.

    2016-01-01

    Chemical bonding is one of the basic concepts in chemistry, and the topic of covalent bonding forms an important core of knowledge for the high school chemistry student. For many teachers it is a challenging concept to teach, not least because it relies mainly on traditional instruction and written work. Similarly, many students find the topic…

  17. Hydrogen Bonding With a Hydrogen Bond: The CH4•••H2O Dimer ...

    Indian Academy of Sciences (India)

    X-H•••C hydrogen bonds in n-alkane-HX (X = F, OH) complexes are stronger than C-H•••X hydrogen bonds. R Parajuli* and E Arunan**. *Department of Physics, Amrit Campus, Tribhuvan University, Kathmandu, Nepal. **Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bengaluru 560012, India.

  18. Chemical Bonding in Solids. On the Generalization of the Concept of Bond Order and Valence for Infinite Periodical Structures

    Czech Academy of Sciences Publication Activity Database

    Ponec, Robert

    2005-01-01

    Roč. 114, 1-3 (2005), s. 208-212 ISSN 1432-881X R&D Projects: GA AV ČR(CZ) IAA4072403 Institutional research plan: CEZ:AV0Z4072921 Keywords : bonding in solids * bond order * valence Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.179, year: 2005

  19. New Insights from Domain-averaged Fermi holes and Bond Order Analysis into the Bonding Conundrum in C2.

    Czech Academy of Sciences Publication Activity Database

    Cooper, D.L.; Ponec, Robert; Kohout, M.

    2016-01-01

    Roč. 114, 7-8 (2016), s. 1270-1284 ISSN 0026-8976 Institutional support: RVO:67985858 Keywords : peculiarity of C2 bonding * domain-averaged Fermi holes (DAFH) * cioslowski bond orders Subject RIV: CC - Organic Chemistry Impact factor: 1.870, year: 2016

  20. 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

  1. An alternative picture of alkali-metal-mediated metallation: cleave and capture chemistry.

    Science.gov (United States)

    Mulvey, Robert E

    2013-05-21

    This perspective article takes an alternative look at alkali-metal-mediated chemistry (exchange of a relatively inert C-H bond for a more reactive C-metal bond by a multicomponent reagent usually containing an alkali metal and a less electropositive metal such as magnesium or zinc). It pictures that the cleavage of selected C-H bonds can be accompanied by the capturing of the generated anion by the multi (Lewis acid)-(Lewis base) character of the residue of the bimetallic base. In this way small atoms or molecules (hydrides, oxygen-based anions) as well as sensitive organic anions (of substituted aromatic compounds, ethers or alkenes) can be captured. Cleave and capture reactions which occur in special positions on the organic substrate are also included.

  2. Understanding Bonds - Denmark

    DEFF Research Database (Denmark)

    Rimmer, Nina Røhr

    2016-01-01

    Undervisningsmateriale. A bond is a debt security, similar to an ”I Owe You document” (IOU). When you purchase a bond, you are lending money to a government, municipality, corporation, federal agency or other entity known as the issuer. In return for the loan, the issuer promises to pay you...... a specified rate of interest during the life of the bond and to repay the face value of the bond (the principal) when it “matures,” or comes due. Among the types of bonds you can choose from are: Government securities, municipal bonds, corporate bonds, mortgage and asset-backed securities, federal agency...... securities and foreign government bonds....

  3. Thai students' mental model of chemical bonding

    Science.gov (United States)

    Sarawan, Supawadee; Yuenyong, Chokchai

    2018-01-01

    This Research was finding the viewing about concept of chemical bonding is fundamental to subsequent learning of various other topics related to this concept in chemistry. Any conceptions about atomic structures that students have will be shown their further learning. The purpose of this study is to interviews conceptions held by high school chemistry students about metallic bonding and to reveal mental model of atomic structures show according to the educational level. With this aim, the questionnaire prepared making use of the literature and administered for analysis about mental model of chemical bonding. It was determined from the analysis of answers of questionnaire the 10th grade, 11th grade and 12th grade students. Finally, each was shown prompts in the form of focus cards derived from curriculum material that showed ways in which the bonding in specific metallic substances had been depicted. Students' responses revealed that learners across all three levels prefer simple, realistic mental models for metallic bonding and reveal to chemical bonding.

  4. Iptycene-based stationary phase with three-dimensional aromatic structure for highly selective separation of H-bonding analytes and aromatic isomers.

    Science.gov (United States)

    Yang, Xiaohong; Han, Ying; Qi, Meiling; Chen, Chuanfeng

    2016-05-06

    Unique structures and molecular recognition ability endow iptycene derivatives with great potential as stationary phases in chromatography, which, however, has not been explored yet. Herein, we report the first example of utilizing a pentiptycene quinone (PQ) for gas chromatographic (GC) separations. Remarkably, the statically coated capillary column with the stationary phase achieved extremely high column efficiency of 4800 plates/m. It exhibited preferential retention and high resolving capability for H-bonding and aromatic analytes and positional isomers, showing advantages over the ordinary polysiloxane phase. Moreover, the fabricated iptycene column showed excellent separation repeatability with RSD values of 0.02-0.06% for intra-day, 0.20-0.35% for inter-day and 3.1-5.5% for between-column, respectively. In conclusion, iptycene derivatives as a new class of stationary phases show promising future for their use in GC separations. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. The new mixed cluster trielide K{sub 3}Ga{sub 11-x}In{sub x} (x = 1.16-1.36). Synthesis, crystal chemistry, and chemical bonding

    Energy Technology Data Exchange (ETDEWEB)

    Falk, Martha; Meyer, Carolin; Roehr, Caroline [Institut fuer Anorganische und Analytische Chemie, Universitaet Freiburg (Germany)

    2017-12-13

    The new cluster compound K{sub 3}Ga{sub 11-x}In{sub x}, which exhibits a very small In/Ga phase width of x = 1.16 to 1.36 only, was obtained in the course of a systematic synthetic, crystallographic and bond theoretical investigation of mixed potassium trielides of the ternary system K-In-Ga. The compound, which was synthesized from nearly stoichiometric amounts of the elements at a maximum temperature of 500 C, crystallizes in a new orthorhombic crystal structure type [space group Cmmm, a = 1577.9(5), b = 3355.1(8), c = 655.2(2) pm, Z = 10, R{sub 1} = 0.0471]. In the complex polyanion, the triels form two crystallographically different [Ga{sub 12}] icosahedra, which are present in a 1:2 ratio, and a previously unknown [M{sub 13}] ''double-cluster'' consisting of two vertex-sharing [M{sub 7}] pentagonal bipyramids. All clusters are connected among each other and via a four-bonded pure In and Ga atom [In(1), Ga(1)]. The polyanion of the compound with the overall formula K{sub 15}M{sub 55} can thus be split up according to [Ga(1X){sub 12}][Ga(2X){sub 12}]{sub 2}[M(3X){sub 13}]In(1){sub 4}Ga(1){sub 2}. Herein, the all-exo bonded closo icosahedra carry a charge of -2, the six four-bonded In/Ga contribute with a charge of -6 and the new [M{sub 13}] ''double-cluster'' thus carries a charge of -3. Under the reasonable assumption of an ''intermediate'' interaction between the two cluster fragments, this charge, i.e. the presence of 15 skeleton electron pairs, is in accordance with the mno electron counting rules. FP-LAPW DFT band structure calculations of two ordered model compounds support this interpretation: The tDOS exhibits a small bandgap and the electron density map suggests a limited additional interaction between the Ga{sub 5} bases of the two bipyramidal cluster fragments. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. Hydrogen Bonds and Life in the Universe

    Directory of Open Access Journals (Sweden)

    Giovanni Vladilo

    2018-01-01

    Full Text Available The scientific community is allocating more and more resources to space missions and astronomical observations dedicated to the search for life beyond Earth. This experimental endeavor needs to be backed by a theoretical framework aimed at defining universal criteria for the existence of life. With this aim in mind, we have explored which chemical and physical properties should be expected for life possibly different from the terrestrial one, but similarly sustained by genetic and catalytic molecules. We show that functional molecules performing genetic and catalytic tasks must feature a hierarchy of chemical interactions operating in distinct energy bands. Of all known chemical bonds and forces, only hydrogen bonds are able to mediate the directional interactions of lower energy that are needed for the operation of genetic and catalytic tasks. For this reason and because of the unique quantum properties of hydrogen bonding, the functional molecules involved in life processes are predicted to have extensive hydrogen-bonding capabilities. A molecular medium generating a hydrogen-bond network is probably essential to support the activity of the functional molecules. These hydrogen-bond requirements constrain the viability of hypothetical biochemistries alternative to the terrestrial one, provide thermal limits to life molecular processes, and offer a conceptual framework to define a transition from a “covalent-bond stage” to a “hydrogen-bond stage” in prebiotic chemistry.

  7. Hydrogen bond dynamics in bulk alcohols

    International Nuclear Information System (INIS)

    Shinokita, Keisuke; Cunha, Ana V.; Jansen, Thomas L. C.; Pshenichnikov, Maxim S.

    2015-01-01

    Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamics–quantum mechanical simulation have established many intriguing features of hydrogen bond dynamics in one of the fundamental solvents in nature, water. The next class of a hydrogen-bonded liquid—alcohols—has attracted much less attention. This is surprising given such important differences between water and alcohols as the imbalance between the number of hydrogen bonds, each molecule can accept (two) and donate (one) and the very presence of the hydrophobic group in alcohols. Here, we use polarization-resolved pump-probe and 2D infrared spectroscopy supported by extensive theoretical modeling to investigate hydrogen bond dynamics in methanol, ethanol, and isopropanol employing the OH stretching mode as a reporter. The sub-ps dynamics in alcohols are similar to those in water as they are determined by similar librational and hydrogen-bond stretch motions. However, lower density of hydrogen bond acceptors and donors in alcohols leads to the appearance of slow diffusion-controlled hydrogen bond exchange dynamics, which are essentially absent in water. We anticipate that the findings herein would have a potential impact on fundamental chemistry and biology as many processes in nature involve the interplay of hydrophobic and hydrophilic groups

  8. Sol-gel bonding of silicon wafers

    International Nuclear Information System (INIS)

    Barbe, C.J.; Cassidy, D.J.; Triani, G.; Latella, B.A.; Mitchell, D.R.G.; Finnie, K.S.; Bartlett, J.R.; Woolfrey, J.L.; Collins, G.A.

    2005-01-01

    Low temperature bonding of silicon wafers was achieved using sol-gel technology. The initial sol-gel chemistry of the coating solution was found to influence the mechanical properties of the resulting bonds. More precisely, the influence of parameters such as the alkoxide concentration, water-to-alkoxide molar ratio, pH, and solution aging on the final bond morphologies and interfacial fracture energy was studied. The thickness and density of the sol-gel coating were characterised using ellipsometry. The corresponding bonded specimens were investigated using attenuated total reflectance Fourier transformed infrared spectroscopy to monitor their chemical composition, infrared imaging to control bond integrity, and cross-sectional transmission electron microscopy to study their microstructure. Their interfacial fracture energy was measured using microindentation. An optimum water-to-alkoxide molar ratio of 10 and hydrolysis water at pH = 2 were found. Such conditions led to relatively dense films (> 90%), resulting in bonds with a fracture energy of 3.5 J/m 2 , significantly higher than those obtained using classical hydrophilic bonding (typically 1.5-2.5 J/m 2 ). Ageing of the coating solution was found to decrease the bond strength

  9. Hydrogen Bonds and Life in the Universe

    Science.gov (United States)

    2018-01-01

    The scientific community is allocating more and more resources to space missions and astronomical observations dedicated to the search for life beyond Earth. This experimental endeavor needs to be backed by a theoretical framework aimed at defining universal criteria for the existence of life. With this aim in mind, we have explored which chemical and physical properties should be expected for life possibly different from the terrestrial one, but similarly sustained by genetic and catalytic molecules. We show that functional molecules performing genetic and catalytic tasks must feature a hierarchy of chemical interactions operating in distinct energy bands. Of all known chemical bonds and forces, only hydrogen bonds are able to mediate the directional interactions of lower energy that are needed for the operation of genetic and catalytic tasks. For this reason and because of the unique quantum properties of hydrogen bonding, the functional molecules involved in life processes are predicted to have extensive hydrogen-bonding capabilities. A molecular medium generating a hydrogen-bond network is probably essential to support the activity of the functional molecules. These hydrogen-bond requirements constrain the viability of hypothetical biochemistries alternative to the terrestrial one, provide thermal limits to life molecular processes, and offer a conceptual framework to define a transition from a “covalent-bond stage” to a “hydrogen-bond stage” in prebiotic chemistry. PMID:29301382

  10. Hydrogen bond dynamics in bulk alcohols.

    Science.gov (United States)

    Shinokita, Keisuke; Cunha, Ana V; Jansen, Thomas L C; Pshenichnikov, Maxim S

    2015-06-07

    Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamics-quantum mechanical simulation have established many intriguing features of hydrogen bond dynamics in one of the fundamental solvents in nature, water. The next class of a hydrogen-bonded liquid--alcohols--has attracted much less attention. This is surprising given such important differences between water and alcohols as the imbalance between the number of hydrogen bonds, each molecule can accept (two) and donate (one) and the very presence of the hydrophobic group in alcohols. Here, we use polarization-resolved pump-probe and 2D infrared spectroscopy supported by extensive theoretical modeling to investigate hydrogen bond dynamics in methanol, ethanol, and isopropanol employing the OH stretching mode as a reporter. The sub-ps dynamics in alcohols are similar to those in water as they are determined by similar librational and hydrogen-bond stretch motions. However, lower density of hydrogen bond acceptors and donors in alcohols leads to the appearance of slow diffusion-controlled hydrogen bond exchange dynamics, which are essentially absent in water. We anticipate that the findings herein would have a potential impact on fundamental chemistry and biology as many processes in nature involve the interplay of hydrophobic and hydrophilic groups.

  11. Hydrogen Bonds and Life in the Universe.

    Science.gov (United States)

    Vladilo, Giovanni; Hassanali, Ali

    2018-01-03

    The scientific community is allocating more and more resources to space missions and astronomical observations dedicated to the search for life beyond Earth. This experimental endeavor needs to be backed by a theoretical framework aimed at defining universal criteria for the existence of life. With this aim in mind, we have explored which chemical and physical properties should be expected for life possibly different from the terrestrial one, but similarly sustained by genetic and catalytic molecules. We show that functional molecules performing genetic and catalytic tasks must feature a hierarchy of chemical interactions operating in distinct energy bands. Of all known chemical bonds and forces, only hydrogen bonds are able to mediate the directional interactions of lower energy that are needed for the operation of genetic and catalytic tasks. For this reason and because of the unique quantum properties of hydrogen bonding, the functional molecules involved in life processes are predicted to have extensive hydrogen-bonding capabilities. A molecular medium generating a hydrogen-bond network is probably essential to support the activity of the functional molecules. These hydrogen-bond requirements constrain the viability of hypothetical biochemistries alternative to the terrestrial one, provide thermal limits to life molecular processes, and offer a conceptual framework to define a transition from a "covalent-bond stage" to a "hydrogen-bond stage" in prebiotic chemistry.

  12. Water at surfaces with tunable surface chemistries

    Science.gov (United States)

    Sanders, Stephanie E.; Vanselous, Heather; Petersen, Poul B.

    2018-03-01

    Aqueous interfaces are ubiquitous in natural environments, spanning atmospheric, geological, oceanographic, and biological systems, as well as in technical applications, such as fuel cells and membrane filtration. Where liquid water terminates at a surface, an interfacial region is formed, which exhibits distinct properties from the bulk aqueous phase. The unique properties of water are governed by the hydrogen-bonded network. The chemical and physical properties of the surface dictate the boundary conditions of the bulk hydrogen-bonded network and thus the interfacial properties of the water and any molecules in that region. Understanding the properties of interfacial water requires systematically characterizing the structure and dynamics of interfacial water as a function of the surface chemistry. In this review, we focus on the use of experimental surface-specific spectroscopic methods to understand the properties of interfacial water as a function of surface chemistry. Investigations of the air-water interface, as well as efforts in tuning the properties of the air-water interface by adding solutes or surfactants, are briefly discussed. Buried aqueous interfaces can be accessed with careful selection of spectroscopic technique and sample configuration, further expanding the range of chemical environments that can be probed, including solid inorganic materials, polymers, and water immiscible liquids. Solid substrates can be finely tuned by functionalization with self-assembled monolayers, polymers, or biomolecules. These variables provide a platform for systematically tuning the chemical nature of the interface and examining the resulting water structure. Finally, time-resolved methods to probe the dynamics of interfacial water are briefly summarized before discussing the current status and future directions in studying the structure and dynamics of interfacial water.

  13. 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...

  14. 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

  15. General chemistry

    International Nuclear Information System (INIS)

    Kwon, Yeong Sik; Lee, Dong Seop; Ryu, Haung Ryong; Jang, Cheol Hyeon; Choi, Bong Jong; Choi, Sang Won

    1993-07-01

    The book concentrates on the latest general chemistry, which is divided int twenty-three chapters. It deals with basic conception and stoichiometry, nature of gas, structure of atoms, quantum mechanics, symbol and structure of an electron of ion and molecule, chemical thermodynamics, nature of solid, change of state and liquid, properties of solution, chemical equilibrium, solution and acid-base, equilibrium of aqueous solution, electrochemistry, chemical reaction speed, molecule spectroscopy, hydrogen, oxygen and water, metallic atom; 1A, IIA, IIIA, carbon and atom IVA, nonmetal atom and an inert gas, transition metals, lanthanons, and actinoids, nuclear properties and radioactivity, biochemistry and environment chemistry.

  16. Radiation chemistry

    International Nuclear Information System (INIS)

    Swallow, A.J.

    1983-01-01

    The subject is covered in chapters, entitled: introduction (defines scope of article as dealing with the chemistry of reactive species, (e.g. excess electrons, excited states, free radicals and inorganic ions in unusual valency states) as studied using radiation with radiation chemistry in its traditional sense and with biological and industrial applications); gases; water and simple inorganic systems; aqueous metallo-organic compounds and metalloproteins; small organic molecules in aqueous solution; microheterogeneous systems; non-aqueous liquids and solutions; solids; biological macromolecules; synthetic polymers. (U.K.)

  17. Basic organometallic chemistry: containing comprehensive bibliography

    National Research Council Canada - National Science Library

    Haiduc, Ionel; Zuckerman, Jerry J

    1985-01-01

    .... Organometallic chemistry is the discipline dealing with compounds containing at least one direct metal-carbon bond. This bond can be simple covalent [as in lead tetraethyl, Pb(C H )J or π-dative [as in ferrocene, Fe(i/ 5 2 5 -C 5 H 5 ) 2 ] or even predominantly ionic [as in ethylsodium, N a + C 2 Hs ]. On this basis, compounds like metal alkoxides, [for example, alu...

  18. The Effectiveness of a Computer-Assisted Instruction Package in Supplementing Teaching of Selected Concepts in High School Chemistry: Writing Formulas and Balancing Chemical Equations.

    Science.gov (United States)

    Wainwright, Camille L.

    Four classes of high school chemistry students (N=108) were randomly assigned to experimental and control groups to investigate the effectiveness of a computer assisted instruction (CAI) package during a unit on writing/naming of chemical formulas and balancing equations. Students in the experimental group received drill, review, and reinforcement…

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

    International Nuclear Information System (INIS)

    1983-01-01

    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.) [pt

  20. Ionic liquid syntheses via click chemistry: expeditious routes toward versatile functional materials.

    Science.gov (United States)

    Mirjafari, Arsalan

    2018-03-25

    Since the introduction of click chemistry by K. B. Sharpless in 2001, its exploration and exploitation has occurred in countless fields of materials sciences in both academic and industrial spheres. Click chemistry is defined as an efficient, robust, and orthogonal synthetic platform for the facile formation of new carbon-heteroatom bonds, using readily available starting materials. Premier examples of click reactions are copper(i)-catalyzed azide-alkyne Huisgen cycloaddition (CuAAC) and the thiol-X (X = ene and yne) coupling reactions to form C-N and C-S bonds, respectively. The emphasis of this review is centered on the rapidly expanding area of click chemistry-mediated synthesis of functional ionic liquids via CuAAC, thiol-X and oxime formation, and selected examples of nucleophilic ring-opening reactions, while offering some thoughts on emerging challenges, opportunities and ultimately the evolution of this field. Click chemistry offers tremendous opportunities, and introduces intriguing perspectives for efficient and robust generation of tailored task-specific ionic liquids - an important class of soft materials.

  1. Structure of selected basic zinc/copper (II) phosphate minerals based upon near-infrared spectroscopy--implications for hydrogen bonding.

    Science.gov (United States)

    Frost, Ray L; Reddy, B Jagannadha; Palmer, Sara J; Keeffe, Eloise C

    2011-03-01

    The NIR spectra of reichenbachite, scholzite and parascholzite have been studied at 298 K. The spectra of the minerals are different, in line with composition and crystal structural variations. Cation substitution effects are significant in their electronic spectra and three distinctly different electronic transition bands are observed in the near-infrared spectra at high wavenumbers in the 12,000-7600 cm(-1) spectral region. Reichenbachite electronic spectrum is characterised by Cu(II) transition bands at 9755 and 7520 cm(-1). A broad spectral feature observed for ferrous ion in the 12,000-9000 cm(-1) region both in scholzite and parascholzite. Some what similarities in the vibrational spectra of the three phosphate minerals are observed particularly in the OH stretching region. The observation of strong band at 5090 cm(-1) indicates strong hydrogen bonding in the structure of the dimorphs, scholzite and parascholzite. The three phosphates exhibit overlapping bands in the 4800-4000 cm(-1) region resulting from the combinations of vibrational modes of (PO(4))(3-) units. Copyright © 2010 Elsevier B.V. All rights reserved.

  2. New decision criteria for selecting delta check methods based on the ratio of the delta difference to the width of the reference range can be generally applicable for each clinical chemistry test item.

    Science.gov (United States)

    Park, Sang Hyuk; Kim, So-Young; Lee, Woochang; Chun, Sail; Min, Won-Ki

    2012-09-01

    Many laboratories use 4 delta check methods: delta difference, delta percent change, rate difference, and rate percent change. However, guidelines regarding decision criteria for selecting delta check methods have not yet been provided. We present new decision criteria for selecting delta check methods for each clinical chemistry test item. We collected 811,920 and 669,750 paired (present and previous) test results for 27 clinical chemistry test items from inpatients and outpatients, respectively. We devised new decision criteria for the selection of delta check methods based on the ratio of the delta difference to the width of the reference range (DD/RR). Delta check methods based on these criteria were compared with those based on the CV% of the absolute delta difference (ADD) as well as those reported in 2 previous studies. The delta check methods suggested by new decision criteria based on the DD/RR ratio corresponded well with those based on the CV% of the ADD except for only 2 items each in inpatients and outpatients. Delta check methods based on the DD/RR ratio also corresponded with those suggested in the 2 previous studies, except for 1 and 7 items in inpatients and outpatients, respectively. The DD/RR method appears to yield more feasible and intuitive selection criteria and can easily explain changes in the results by reflecting both the biological variation of the test item and the clinical characteristics of patients in each laboratory. We suggest this as a measure to determine delta check methods.

  3. Perspectives on halogen bonding and other sigma-hole interactions: Lex parsimoniae (Occam's Razor)

    Czech Academy of Sciences Publication Activity Database

    Politzer, P.; Riley, Kevin Eugene; Bulat, F. A.; Murray, J. S.

    2012-01-01

    Roč. 998, SI (2012), s. 2-8 ISSN 2210-271X Institutional research plan: CEZ:AV0Z40550506 Keywords : halogen bonding * alpha-Hole bonding * hydrogen bonding * electrostatics /polarization * dispersion * electrostatic potentials Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.139, year: 2012

  4. Handbook of heterocyclic chemistry

    National Research Council Canada - National Science Library

    Katritzky, Alan R

    2010-01-01

    ... Heterocyclic Chemistry I (1984) Comprehensive Heterocyclic Chemistry II (1996) Comprehensive Heterocyclic Chemistry III (2008) Comprehensive Organic Functional Group Transformations I (1995) Compreh...

  5. 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.

  6. Chemistry Notes

    Science.gov (United States)

    School Science Review, 1972

    1972-01-01

    Short articles on the kinetics of the hydrogen peroxide-iodide ion reaction, simulation of fluidization catalysis, the use of Newman projection diagrams to represent steric relationships in organic chemistry, the use of synthetic substrates for proteolytic enzyme reactions, and two simple clock reactions"--hydrolysis of halogenoalkanes and…

  7. Elaboration of Copper-Oxygen Mediated C–H Activation Chemistry in Consideration of Future Fuel and Feedstock Generation

    Science.gov (United States)

    Lee, Jung Yoon; Karlin, Kenneth D

    2015-01-01

    To contribute solutions for current energy concerns, improvements in the efficiency of C-H bond cleavage chemistry, e.g., selective oxidation of methane to methanol, could minimize losses in natural gas usage or produce feedstocks for fuels. Oxidative C-H activation is also a component of polysaccharide degradation, affording alternative biofuels from abundant biomass. Thus, an understanding of active-site chemistry in copper monooxygenases, those activating strong C-H bonds is briefly reviewed. Then, recent advances in the synthesis-generation and study of various copper-oxygen intermediates are highlighted. Of special interest are cupric-superoxide, Cu-hydroperoxo and Cu-oxy complexes. Such investigations can contribute to an enhanced future application of C-H oxidation or oxygenation processes using air, as concerning societal energy goals. PMID:25756327

  8. Activation of the C-H bond: catalytic hydroxylation of hydrocarbons by new cobaltic alkylperoxydic complexes; selective and catalytic cycloalkane dehydrogenation in presence of uranium for hydrogen transfer

    International Nuclear Information System (INIS)

    Brazi, E.

    1987-01-01

    The aim of the thesis is to improve efficiency and selectivity of chemical reactions for alkane transformations. In the first part decomposition of hydroperoxides and hydrocarbon hydroxylation by cobalt complexes is studied. In the second part cycloalkanes are dehydrogenated into aromatics with a Pt catalyst, trapping hydrogen by uranium. Uranium hydride UH 3 can yield very pure hydrogen at reasonable temperature [fr

  9. Studies on the selectivity of the reaction of (CO){sub 5}W=C(aryl)H with enynes: transfer of the carbene ligand to the C=C Bond versus insertion of the C triple bond C into the W=C Bond

    Energy Technology Data Exchange (ETDEWEB)

    Fischer, H.; Volkland, H.P.; Stumpf, R.

    1996-10-01

    The strongly electrophilic monophenylcarbene complex [(CO){sub 5}W=C(Ph)H] (2a) reacts with the enynes H-C triple bond C-R(R=-C(Me)=CH{sub 2})(3), -C{sub 6}H{sub 4}-CH=CH{sub 2}-p (5) and subsequently with PMe{sub 3} to form the C{sub a}lpha-PMe{sub 3} adducts of the vinylidene complexes [(CO){sub 5}W-{l_brace}C(PMe{sub 3})=CH-C{sub 3}H{sub 3}(Me)Ph{r_brace}] (4) and [(CO){sub 5}W {l_brace}C(PMe{sub 3})=CH-C{sub 6}H{sub 4}-C{sub 3}H{sub 4}Ph{r_brace}] (6). The reaction very likely proceeds by transfer of the carbene ligand to the C=C bond of the enyne to form a cyclopropyl-substituted alkyne complex which is in equilibrium with its vinylidene isomer.

  10. π-Bond Screening in Benzonorbornadienes: The Role of 7-Substituents in Governing the Facial Selectivity for the Diels-Alder Reaction of Benzonorbornadienes with 3,6-Di(2-pyridyl-s-Tetrazine

    Directory of Open Access Journals (Sweden)

    Peter A. Harrison

    2001-03-01

    Full Text Available Benzonorbornadiene 21, 7-spirocyclopropylbenzonorbornadiene 23, 7,7-dimethylbenzonorbornadiene 25, and 7-spirocyclopentylbenzonorbornadiene 27 have been reacted with 3,6-di(2-pyridyl-s-tetrazine (rate: 21>23>25=27 to form symmetrical 4,5-dihydropyridazines which are stable towards fragmentation but rearrange with varying facility to their 1,4 isomers. The facial selectivity of attack on the π-bond changes from exo-attack for 21 and 23 to endo-attack for 25 and 27. The 7-spirocyclopropyl benzonorbornadiene 23 typically forms a mixture of dihydropyridazines with exo-stereochemistry, which undergo further stereochemical isomerisation to an exo-fused product upon acetylation (acetyl chloride in hot pyridine. Oxidation with DDQ of the dihydropyridazines individually or as mixtures gives the corresponding fused 3,6-di(2-pyridylpyridazines.

  11. Nb{sub 2}OsB{sub 2}, with a new twofold superstructure of the U{sub 3}Si{sub 2} type: Synthesis, crystal chemistry and chemical bonding

    Energy Technology Data Exchange (ETDEWEB)

    Mbarki, Mohammed; Touzani, Rachid St.; Fokwa, Boniface P.T., E-mail: boniface.fokwa@ac.rwth-aachen.de

    2013-07-15

    The new ternary metal-rich boride, Nb{sub 2}OsB{sub 2}, was synthesized by arc-melting the elements in a water-cooled copper crucible under an argon atmosphere. The compound was characterized from single-crystal X-ray data and EDX measurements. It crystallizes as a new superstructure (space group P4/mnc, no. 128) of the tetragonal U{sub 3}Si{sub 2}-structure type with lattice parameters a=5.922(1) Å and c=6.879(2) Å. All of the B atoms are involved in B{sub 2} dumbbells with B–B distances of 1.89(4) Å. Structure relaxation using VASP (Vienna ab intio Simulation Package) has confirmed the space group and the lattice parameters. According to electronic structure calculations (TB–LMTO–ASA), the homoatomic B–B interactions are optimized and very strong, but relatively strong heteroatomic Os–B, Nb–B and Nb–Os bonds are also found: These interactions, which together build a three-dimensional network, are mainly responsible for the structural stability of this new phase. The density of state at the Fermi level predicts metallic behavior, as expected, from this metal-rich boride. - Graphical abstract: Nb{sub 2}OsB{sub 2} is, to the best of our knowledge, the first fully characterized phase in the ternary Nb–Os–B system. It crystallizes (space group P4/mnc, 128) with a new twofold superstructure of the U{sub 3}Si{sub 2} structure type (space group P4/mbm, 127), and is therefore the first boride in this structure family crystallizing with a superstructure of the U{sub 3}Si{sub 2} structure type. We show that the distortions leading to this superstructure occurs mainly in the Nb-layer, which tries to accommodate the large osmium atoms. The consequence of this puckering is the building osmium dumbbells instead of chains along [001]. - Highlights: • First compound in the Nb–Os–B system. • New twofold superstructure of U{sub 3}Si{sub 2} structure type. • Puckering of Nb-layer responsible for superstructure occurrence. • Chemical bonding studied

  12. 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

  13. Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions

    International Nuclear Information System (INIS)

    Gruner, B.; Plesek, J.; Baca, J.; Cisarova, I.; Dozol, J.F.; Rouquette, H.; Vinas, C.; Selucky, P.; Rais, J.

    2002-01-01

    A new series of boron substituted cobalt bis(dicarbollide)(1-) ion (1) derivatives of the general formula [(8-CMPO-(CH 2 -CH 2 O) 2 -1,2-C 2 B 9 H 10 )(1',2'-C 2 B 9 H 11 )-3,3'-Co] - (CMPO = Ph 2 P(O)-CH 2 C(O)NR, R = C 4 H 9 (3b), -C 12 H 25 (4b), -CH 2 -C 6 H 5 (5b)) was prepared by ring cleavage of the 8-dioxane-cobalt bis(dicarbollide) (2) bi-polar compound by the respective primary amines and by subsequent reaction of the resulting amino derivatives (3a-5a) with the nitrophenyl ester of diphenyl-phosphoryl-acetic acid. The compounds were synthesized with the aim to develop a new class of more efficient extraction agents for liquid/liquid extraction of polyvalent cations, i.e. lanthanides and actinides, from high-level activity nuclear waste. All compounds were characterized by a combination of 11 B NMR, 1 H high field NMR, Mass Spectrometry with Electro-spray and MALDI TOF ionisation, HPLC and other techniques. The molecular structure of the supramolecular Ln 3+ complex of the anion 5b was determined by single crystal X-ray diffraction analysis. Crystallographic results proved that the Ln(m) atom is bonded to three functionalized cobalt bis(dicarbollide) anions in a charge compensated complex. The cation is tightly coordinated by six oxygen atoms of the CMPO terminal groups (two of each ligand) and by three water molecules completing the metal coordination number to 9. Atoms occupying the primary coordination sphere form a tri-capped trigonal prismatic arrangement. Very high liquid-liquid extraction efficiency of all anionic species was observed. Moreover, less polar toluene can be applied as an auxiliary solvent replacing the less environmentally friendly nitro- and chlorinated solvents used in the current dicarbollide liquid-liquid extraction process. The extraction coefficients are sufficiently high for possible technological applications. (authors)

  14. Radiopharmaceutical chemistry for positron emission tomography

    NARCIS (Netherlands)

    Elsinga, PH

    Radiopharmaceutical chemistry includes the selection, preparation, and preclinical evaluation of radiolabeled compounds. This paper describes selection criteria for candidates for positron emission tomography (PET) investigations. Practical aspects of nucleophilic and electrophilic

  15. 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.

  16. Bioactive Natural Product and Superacid Chemistry for Lead Compound Identification: A Case Study of Selective hCA III and L-Type Ca2+ Current Inhibitors for Hypotensive Agent Discovery

    Directory of Open Access Journals (Sweden)

    Hélène Carreyre

    2017-05-01

    Full Text Available Dodoneine (Ddn is one of the active compounds identified from Agelanthus dodoneifolius, which is a medicinal plant used in African pharmacopeia and traditional medicine for the treatment of hypertension. In the context of a scientific program aiming at discovering new hypotensive agents through the original combination of natural product discovery and superacid chemistry diversification, and after evidencing dodoneine’s vasorelaxant effect on rat aorta, superacid modifications allowed us to generate original analogues which showed selective human carbonic anhydrase III (hCA III and L-type Ca2+ current inhibition. These derivatives can now be considered as new lead compounds for vasorelaxant therapeutics targeting these two proteins.

  17. Activation analysis in water chemistry

    International Nuclear Information System (INIS)

    Szabo, A.; Toth, A.

    1978-01-01

    The potential applications of activation analysis in water chemistry are discussed. The principle, unit operations, the radiation sources and measuring instruments of activation analysis are described. The sensitivity of activation analysis is given in tabulated form for some elements of major importance in water chemistry and the elements readily accessible to determination by measurement of the spontaneous gamma radiation are listed. A few papers selected from the recent international professional literature are finally reviewed, in which the authors report on the results obtained by activation analysis applied to water chemistry. (author)

  18. 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.

  19. Chemistry and physics

    International Nuclear Information System (INIS)

    Broerse, J.J.; Barendsen, G.W.; Kal, H.B.; Kogel, A.J. van der

    1983-01-01

    This book contains the extended abstracts of the contributions of the poster workshop sessions on chemistry and physics of the 7th international congress of radiation research. They cover the following main topics: primary processes in radiation physics and chemistry, general chemistry in radiation chemistry, DNA and model systems in radiation chemistry, molecules of biological interest in radiation chemistry, techniques in radiation chemistry, hot atom chemistry. refs.; figs.; tabs

  20. A Global Stock and Bond Model

    OpenAIRE

    Connor, Gregory

    1996-01-01

    Factor models are now widely used to support asset selection decisions. Global asset allocation, the allocation between stocks versus bonds and among nations, usually relies instead on correlation analysis of international equity and bond indexes. It would be preferable to have a single integrated framework for both asset selection and asset allocation. This framework would require a factor model applicable at an asset or country level, as well as at a global level,...

  1. Chemistry of the actinide elements. Second edition

    International Nuclear Information System (INIS)

    Katz, J.J.; Seaborg, G.T.; Morss, L.R.

    1987-01-01

    This is an exhaustive, updated discourse on the chemistry of Actinides, Volume 1 contains a systematic coverage of the elements Ac, Th, Pa, U, Np, and Pu, which constitutes Part 1 of the work. The characterization of each element is discussed in terms of its nuclear properties, occurrence, preparation, atomic and metallic properties, chemistry of specific compounds, and solution chemistry. The first part of Volume 2 follows the same format as Volume 1 but is confined to the elements Am, Cm, Bk, Cf, and Es, plus a more condensed coverage of the Transeinsteinium elements (Fm, Md, No, Lw, and 104-109). Part 2 of this volume is devoted to a discussion of the actinide elements in general, with a specific focus on electronic spectra, thermodynamic and magnetic properties, the metallic state, structural chemistry, solution kinetics, organometallic chemistry for σ- and π-bonded compounds, and some concluding remarks on the superheavy elements

  2. Radioanalytical chemistry

    International Nuclear Information System (INIS)

    1982-01-01

    The bibliography of Hungarian literature in the field of radioanalytical chemistry covers the four-year period 1976-1979. The list of papers contains 290 references in the alphabetical order of the first authors. The majority of the titles belongs to neutron activation analysis, labelling, separation and determination of radioactive isotopes. Other important fields like radioimmunoassay, environmental protection etc. are covered as well. (Sz.J.)

  3. Analytical chemistry

    International Nuclear Information System (INIS)

    Anon.

    1985-01-01

    The division for Analytical Chemistry continued to try and develope an accurate method for the separation of trace amounts from mixtures which, contain various other elements. Ion exchange chromatography is of special importance in this regard. New separation techniques were tried on certain trace amounts in South African standard rock materials and special ceramics. Methods were also tested for the separation of carrier-free radioisotopes from irradiated cyclotron discs

  4. Industrial chemistry engineering

    International Nuclear Information System (INIS)

    1993-01-01

    This book on industrial chemistry engineering is divided in two parts. The first part deals with industrial chemistry, inorganic industrial chemistry, organic industrial chemistry, analytical chemistry and practical questions. The last parts explain the chemical industry, a unit parts and thermodynamics in chemical industry and reference. It reveals the test subjects for the industrial chemistry engineering with a written examination and practical skill.

  5. Green chemistry

    International Nuclear Information System (INIS)

    Warner, John C.; Cannon, Amy S.; Dye, Kevin M.

    2004-01-01

    A grand challenge facing government, industry, and academia in the relationship of our technological society to the environment is reinventing the use of materials. To address this challenge, collaboration from an interdisciplinary group of stakeholders will be necessary. Traditionally, the approach to risk management of materials and chemicals has been through inerventions intended to reduce exposure to materials that are hazardous to health and the environment. In 1990, the Pollution Prevention Act encouraged a new tact-elimination of hazards at the source. An emerging approach to this grand challenge seeks to embed the diverse set of environmental perspectives and interests in the everyday practice of the people most responsible for using and creating new materials--chemists. The approach, which has come to be known as Green Chemistry, intends to eliminate intrinsic hazard itself, rather than focusing on reducing risk by minimizing exposure. This chapter addresses the representation of downstream environmental stakeholder interests in the upstream everyday practice that is reinventing chemistry and its material inputs, products, and waste as described in the '12 Principles of Green Chemistry'

  6. Welding, Bonding and Fastening, 1984

    Science.gov (United States)

    Buckley, J. D. (Editor); Stein, B. A. (Editor)

    1985-01-01

    A compilation of papers presented in a joint NASA, American Society for Metals, The George Washington University, American Welding Soceity, and Society of Manufacturing Engineers conference on Welding, Bonding, and Fastening at Langley Research Center, Hampton, VA, on October 23 to 25, 1984 is given. Papers were presented on technology developed in current research programs relevant to welding, bonding, and fastening of structural materials required in fabricating structures and mechanical systems used in the aerospace, hydrospace, and automotive industries. Topics covered in the conference included equipment, hardware and materials used when welding, brazing, and soldering, mechanical fastening, explosive welding, use of unique selected joining techniques, adhesives bonding, and nondestructive evaluation. A concept of the factory of the future was presented, followed by advanced welding techniques, automated equipment for welding, welding in a cryogenic atmosphere, blind fastening, stress corrosion resistant fasteners, fastening equipment, explosive welding of different configurations and materials, solid-state bonding, electron beam welding, new adhesives, effects of cryogenics on adhesives, and new techniques and equipment for adhesive bonding.

  7. Bonding with Your Baby

    Science.gov (United States)

    ... the future bonding of the child and parent. Adoptive parents may be concerned about bonding with their ... general emotional support. And it's OK to ask family members and friends for help in the days — ...

  8. Gas-phase ion/ion reactions of peptides and proteins: acid/base, redox, and covalent chemistries.

    Science.gov (United States)

    Prentice, Boone M; McLuckey, Scott A

    2013-02-01

    Gas-phase ion/ion reactions are emerging as useful and flexible means for the manipulation and characterization of peptide and protein biopolymers. Acid/base-like chemical reactions (i.e., proton transfer reactions) and reduction/oxidation (redox) reactions (i.e., electron transfer reactions) represent relatively mature classes of gas-phase chemical reactions. Even so, especially in regards to redox chemistry, the widespread utility of these two types of chemistries is undergoing rapid growth and development. Additionally, a relatively new class of gas-phase ion/ion transformations is emerging which involves the selective formation of functional-group-specific covalent bonds. This feature details our current work and perspective on the developments and current capabilities of these three areas of ion/ion chemistry with an eye towards possible future directions of the field.

  9. Australia's Bond Home Bias

    OpenAIRE

    Anil V. Mishra; Umaru B. Conteh

    2014-01-01

    This paper constructs the float adjusted measure of home bias and explores the determinants of bond home bias by employing the International Monetary Fund's high quality dataset (2001 to 2009) on cross-border bond investment. The paper finds that Australian investors' prefer investing in countries with higher economic development and more developed bond markets. Exchange rate volatility appears to be an impediment for cross-border bond investment. Investors prefer investing in countries with ...

  10. 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.

  11. Comparative evaluation of shear bond strength of metallic brackets bonded with two different bonding agents under dry conditions and with saliva contamination.

    Science.gov (United States)

    Khanehmasjedi, Mashallah; Naseri, Mohammad Ali; Khanehmasjedi, Samaneh; Basir, Leila

    2017-02-01

    This study compared the shear bond strength of metallic brackets bonded with Single Bond and Assure bonding agents under dry and saliva-contamination conditions. Sixty sound premolar teeth were selected, and stainless-steel brackets were bonded on enamel surfaces with Single Bond and Assure bonding agents under dry condition or with saliva contamination. Shear bond strength values of brackets were measured in a universal testing machine. The adhesive remnant index scores were determined after debonding of the brackets under a stereomicroscope. One-way analysis of variance (ANOVA) was used to analyze bond strength. Two-by-two comparisons were made with post hoc Tukey tests (pbrackets to tooth structure were 9.29±8.56 MPa and 21.25±8.93 MPa with the use of Assure resin bonding agent under saliva-contamination and dry conditions, respectively. These values were 10.13±6.69 MPa and 14.09±6.6 MPa, respectively, under the same conditions with the use of Single Bond adhesive. Contamination with saliva resulted in a significant decrease in the bond strength of brackets to tooth structure with the application of Assure adhesive resin (pbrackets to tooth structures. Contamination with saliva significantly decreased the bond strength of Assure bonding agent compared with dry conditions. Copyright © 2016. Published by Elsevier Taiwan LLC.

  12. Bonded stacked-ring insulator for the Antares electron gun

    International Nuclear Information System (INIS)

    Stine, R.D.; Allen, G.R.; Eaton, E.; Weinstein, B.

    1982-01-01

    A large diameter insulator utilizing epoxy bonding which has sufficient mechanical strength to support the 3000 kg cathode/grid assembly was developed. Bonding the insulator simplifies the handling and reduces the number of 0-ring seals to a minimum. We have described the material selection, bonding techniques and electrical design approach

  13. Phenylacetylene and H bond

    Indian Academy of Sciences (India)

    ... all resembling H bonds. Non-linear H bonds due to secondary interactions. C-H stretching frequency shows blue shift. Heavy atom distances are longer than the sum of van der Waals radii. Formed a task group through IUPAC to come up with a modern definition of H bond. 15 international experts including Desiraju.

  14. 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

  15. The phosphorus and the transition metals chemistry

    International Nuclear Information System (INIS)

    Mathey, F.

    1988-01-01

    The 1988 progress report, concerning the Polytechnic School unit (France), which studies the phosphorus and the transition metals chemistry, is presented. The laboratory activities are related to the following topics: the phosporus heterocyclic chemistry, the phosphorus-carbon double bonds chemistry, the new transition metals phosphorus compounds, the phosphonates and their uses. Some practical applications of homogeneous catalysis and new materials synthesis are investigated. The main results obtained are: the discovery of the tetra-phosphafulvalenes, the utilization of a new synthesis method of the phosphorus-carbon double bonds and the stabilization of the α-phosphonyled carbanions by the lithium diisopropylamidourea. The papers, the congress communications and the thesis are also shown [fr

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

    Science.gov (United States)

    Stewart, Mikaela; Dunlap, Tori; Dourlain, Elizabeth; Grant, Bryce; McFail-Isom, Lori

    2013-01-01

    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.

  17. Enamel and dentin bond strength following gaseous ozone application.

    Science.gov (United States)

    Cadenaro, Milena; Delise, Chiara; Antoniollo, Francesca; Navarra, Ottavia Chiara; Di Lenarda, Roberto; Breschi, Lorenzo

    2009-08-01

    To evaluate the effects of gaseous ozone application on enamel and dentin bond strength produced by two self-etching adhesive systems. The shear bond strength test was conducted to assess adhesion on enamel (protocol 1), while the microtensile bond strength test was performed on dentin (protocol 2). Protocol 1: 96 bovine incisors were randomly divided into 4 groups, and enamel surfaces were bonded in accordance with the following treatments: (1E) ozone + Clearfil Protect Bond; (2E) Clearfil Protect Bond (control); (3E) ozone + Xeno III; (4E) Xeno III (control). Ozone gas was applied for 80 s. Shear bond strength was measured with a universal testing machine. Protocol 2: 40 noncarious human molars were selected. Middle/deep dentin was exposed and bonded in accordance with the following treatments: (1D) ozone+Clearfil Protect Bond; (2D) Clearfil Protect Bond (control); (3D) ozone+Xeno III (4D) Xeno III (control). Four-mm-thick buildups were built on the adhesives, then specimens were sectioned in accordance with the nontrimming technique. Specimens were stressed until failure occurred, and failure modes were analyzed. Shear bond and microtensile bond strength data were analyzed using two-way ANOVA and Tukey's post-hoc test. No statistical differences were found between ozone treated specimens and controls, neither on enamel nor on dentin irrespective of the tested adhesive. Clearfil Protect Bond showed higher bond strength to enamel than Xeno III, irrespective of the ozone treatment (p enamel and dentin bond strength.

  18. The 3,7-diazabicyclo[3.3.1]nonane scaffold for subtype selective nicotinic acetylcholine receptor (nAChR) ligands. Part 1: the influence of different hydrogen bond acceptor systems on alkyl and (hetero)aryl substituents.

    Science.gov (United States)

    Eibl, Christoph; Tomassoli, Isabelle; Munoz, Lenka; Stokes, Clare; Papke, Roger L; Gündisch, Daniela

    2013-12-01

    3,7-Diazabicyclo[3.3.1]nonane is a naturally occurring scaffold interacting with nicotinic acetylcholine receptors (nAChRs). When one nitrogen of the 3,7-diazabicyclo[3.3.1]nonane scaffold was implemented in a carboxamide motif displaying a hydrogen bond acceptor (HBA) functionality, compounds with higher affinities and subtype selectivity for α4β2(∗) were obtained. The nature of the HBA system (carboxamide, sulfonamide, urea) had a strong impact on nAChR interaction. High affinity ligands for α4β2(∗) possessed small alkyl chains, small un-substituted hetero-aryl groups or para-substituted phenyl ring systems along with a carboxamide group. Electrophysiological responses of selected 3,7-diazabicyclo[3.3.1]nonane derivatives to Xenopus oocytes expressing various nAChR subtypes showed diverse activation profiles. Compounds with strongest agonistic profiles were obtained with small alkyl groups whereas a shift to partial agonism/antagonism was observed for aryl substituents. Copyright © 2013 Elsevier Ltd. All rights reserved.

  19. Solution chemistry

    Energy Technology Data Exchange (ETDEWEB)

    None

    1973-07-01

    Research progress is reported on studies in heavy element chemistry. Topics considered are: synergistic complexes of plutonyl ion; water uptake in synergistic systems; formation constants of some uranyl BETA -diketone complexes; thermodynamic acid dissociation constants of BETA -diketones; thermodynamic formation constants of uranyl BETA -diketonates; thiocyanate complexes of some trivalent lanthanides and actinides; stability constants of actinide complexes using dinonyl naphthalenesulfonic acid extraction; TBP extraction of actinides; stability constants of complexes of Pu(III) with 5- sulfosalicycllc acid; and solvent extraction behavior of Pu( VII). (DHM)

  20. Interstellar chemistry.

    Science.gov (United States)

    Klemperer, William

    2006-08-15

    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 observed is a challenge for complete understanding. The role and nature of reactions involving grain surfaces as well as new spectroscopic observations of interstellar and circumstellar regions are topics presented in this special feature.

  1. Manufacturing and sustainability of bonding systems for grinding tools

    OpenAIRE

    Linke, B

    2016-01-01

    © 2016, German Academic Society for Production Engineering (WGP). Grinding and honing processes are quality-defining operations in the production of many modern products. Process performance and product quality are contingent on selecting the correct abrasive tool for a specific application. Thus, tools with different bonding systems are used, namely resin bonded tools, vitrified bonded tools, and metallic bonded tools. Tool manufacturers have great knowledge in the choice and intricate prod...

  2. PWR secondary water chemistry study

    International Nuclear Information System (INIS)

    Pearl, W.L.; Sawochka, S.G.

    1977-02-01

    Several types of corrosion damage are currently chronic problems in PWR recirculating steam generators. One probable cause of damage is a local high concentration of an aggressive chemical even though only trace levels are present in feedwater. A wide variety of trace chemicals can find their way into feedwater, depending on the sources of condenser cooling water and the specific feedwater treatment. In February 1975, Nuclear Water and Waste Technology Corporation (NWT), was contracted to characterize secondary system water chemistry at five operating PWRs. Plants were selected to allow effects of cooling water chemistry and operating history on steam generator corrosion to be evaluated. Calvert Cliffs 1, Prairie Island 1 and 2, Surry 2, and Turkey Point 4 were monitored during the program. Results to date in the following areas are summarized: (1) plant chemistry variations during normal operation, transients, and shutdowns; (2) effects of condenser leakage on steam generator chemistry; (3) corrosion product transport during all phases of operation; (4) analytical prediction of chemistry in local areas from bulk water chemistry measurements; and (5) correlation of corrosion damage to chemistry variation

  3. Ionic Liquids as a Basis Context for Developing High school Chemistry Teaching Materials

    Science.gov (United States)

    Hernani; Mudzakir, A.; Sumarna, O.

    2017-02-01

    This research aims to produce a map of connectedness highschool chemical content with the context of the modern chemical materials applications based on ionic liquids. The research method is content analysis of journal articles related to the ionic liquid materials and the textbooks of high school chemistry and textbooks of general chemistry at the university. The instrument used is the development format of basic text that connect and combine content and context. The results showed the connectedness between: (1) the context lubricants ionic liquid with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, the elements of main group, the elements of transition group, and the classification of macromolecules; (2) the context of fuel cell electrolite with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, Volta cell, and electrolysis cell; (3) the contect of nanocellulose with the content of ionic bonding, covalent bonding, metal bonding, interaction between the particles of matter, colloid, carbon compound, and the classification of macromolecules; and (4) the context of artificial muscle system with the content of ionic bond, covalent bond, metal bonding, interaction between the particles of matter, hydrocarbons, electrolytes and non-electrolytes, and the classification of macromolecules. Based on the result of this content analysis, the context of ionic liquid is predicted can be utilized for the enrichment of high school chemistry and has the potential to become teaching material’s context of high school chemistry in the future.

  4. Teacher Assessment of Practical Skills in A-Level Chemistry

    Science.gov (United States)

    Wood, R.; Ferguson, Carolyn M.

    1975-01-01

    Discusses a two-year assessment undertaken to evaluate the Nuffield A-Level chemistry course. Secondary teachers selected chemistry experiments for assessment purposes and assessed their students in manipulative skills, observational skills, interpretation skills, creative skills, and attitudes. (MLH)

  5. Gas to liquid to solid transition in halogen hot atom chemistry. 6. Product formation routes and chemical selectivity of high energy iodine reactions with butyne isomers

    International Nuclear Information System (INIS)

    Garmestani, S.K.; Firouzbakht, M.L.; Rack, E.P.

    1979-01-01

    Reactions of recoil produced iodine-128 with isomers of butyne were studied in gaseous, high pressure, and condensed phase conditions, with rare gas additives and in the presence and absence of radical scavengers (I 2 and O 2 ). It was found that recoil iodine-128 reactions were initiated by thermal electronically excited I + species for both 1-butyne and 2-butyne systems. While the diverse and complex nature of the reactions cannot be explained by simple chemical parameters, comparisons among the alkyne systems demonstrate preferential attack of iodine at the triple bond resulting, mainly, in electronically excited intermediates. A comparison of the various product formation routes results in the characterization of general traits common to the alkynes. 6 figures, 4 tables

  6. Radiation chemistry and bioradical chemistry

    International Nuclear Information System (INIS)

    Ferradini, C.

    1991-01-01

    Oxygen metabolism results, at the cellular level, in the formation of superoxyde radical O 2 - · and probably also of hydroxyl radical OH·. Other radical species can be produced from exogenous or endogenous molecules and nearly all of them have the possibility to react with oxygen giving peroxyradicals. Some of these transients play a role in various biological processes such as phagocytosis, inflammation or ischemy although the mechanisms invoked are poorly understood. Radiation chemistry is an invaluable tool for obtaining a quantitative view of these mechanisms. A description is given of this interaction [fr

  7. Competition between Halogen, Hydrogen and Dihydrogen Bonding in Brominated Carboranes

    Czech Academy of Sciences Publication Activity Database

    Fanfrlík, Jindřich; Holub, Josef; Růžičková, Z.; Řezáč, Jan; Lane, P. D.; Wann, D. A.; Hnyk, Drahomír; Růžička, A.; Hobza, Pavel

    2016-01-01

    Roč. 17, č. 21 (2016), s. 3373-3376 ISSN 1439-4235 R&D Projects: GA ČR(CZ) GBP208/12/G016; GA ČR(CZ) GA15-05677S Institutional support: RVO:61388963 ; RVO:61388980 Keywords : bromine * carboranes * halogen bonds * sigma holes * X-ray crystal structure Subject RIV: CF - Physical ; Theoretical Chemistry; CA - Inorganic Chemistry (UACH-T) Impact factor: 3.075, year: 2016

  8. Fundamentals of nuclear chemistry

    International Nuclear Information System (INIS)

    Majer, K.

    1982-01-01

    The textbook is a Czech-to-German translation of the second revised edition and covers the subject under the headings: general nuclear chemistry, methods of nuclear chemistry, preparative nuclear chemistry, analytical nuclear chemistry, and applied chemistry. The book is especially directed to students

  9. Astronomical chemistry.

    Science.gov (United States)

    Klemperer, William

    2011-01-01

    The discovery of polar polyatomic molecules in higher-density regions of the interstellar medium by means of their rotational emission detected by radioastronomy has changed our conception of the universe from essentially atomic to highly molecular. We discuss models for molecule formation, emphasizing the general lack of thermodynamic equilibrium. Detailed chemical kinetics is needed to understand molecule formation as well as destruction. Ion molecule reactions appear to be an important class for the generally low temperatures of the interstellar medium. The need for the intrinsically high-quality factor of rotational transitions to definitively pin down molecular emitters has been well established by radioastronomy. The observation of abundant molecular ions both positive and, as recently observed, negative provides benchmarks for chemical kinetic schemes. Of considerable importance in guiding our understanding of astronomical chemistry is the fact that the larger molecules (with more than five atoms) are all organic.

  10. Reburning chemistry

    International Nuclear Information System (INIS)

    Kilpin, P.; Hupa, M.; Glarborg, P.

    1992-01-01

    No reduction chemistry in natural gas (methane) reburning was studied using detailed kinetic modeling. A reaction set including 225 reversible elementary gas-phase reactions and 48 chemical species was applied to an ideal plug flow reactor, and the most important reactions leading to NO reduction were identified and quantified for a number of conditions relevant for natural gas reburning. In addition, the influence of different process parameters on the NO reduction was investigated in the reburn zone and burn-out zone, respectively. Further, comparison of the calculations to available laboratory-scale data on reburning is made. In this paper, the impact of various fluid dynamic, mixing, and chemical effects---not accounted for in the calculations---on the NO reduction and the optimum reburning conditions predicted is discussed

  11. 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).

  12. Origin of the X-Hal (Hal ) Cl, Br) Bond-Length Change in the Halogen-Bonded Complexes

    Czech Academy of Sciences Publication Activity Database

    Wang, Weizhou; Hobza, Pavel

    2008-01-01

    Roč. 112, č. 17 (2008), s. 4114-4119 ISSN 1089-5639 R&D Projects: GA MŠk LC512; GA AV ČR IAA400550510 Institutional research plan: CEZ:AV0Z40550506 Keywords : hal ogen bonded complexes * MP2(full)/6-311++G(d,p) method * natural bond orbital analysis Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.871, year: 2008

  13. 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

    2014-01-07

    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.

  14. N-O chemistry for antibiotics: discovery of N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds as selective antibacterial agents using nitroso Diels-Alder and ene chemistry.

    Science.gov (United States)

    Wencewicz, Timothy A; Yang, Baiyuan; Rudloff, James R; Oliver, Allen G; Miller, Marvin J

    2011-10-13

    The discovery, syntheses, and structure-activity relationships (SAR) of a new family of heterocyclic antibacterial compounds based on N-alkyl-N-(pyridin-2-yl)hydroxylamine scaffolds are described. A structurally diverse library of ∼100 heterocyclic molecules generated from Lewis acid-mediated nucleophilic ring-opening reactions with nitroso Diels-Alder cycloadducts and nitroso ene reactions with substituted alkenes was evaluated in whole cell antibacterial assays. Compounds containing the N-alkyl-N-(pyridin-2-yl)hydroxylamine structure demonstrated selective and potent antibacterial activity against the Gram-positive bacterium Micrococcus luteus ATCC 10240 (MIC(90) = 2.0 μM or 0.41 μg/mL) and moderate activity against other Gram-positive strains including antibiotic resistant strains of Staphylococcus aureus (MRSA) and Enterococcus faecalis (VRE). A new synthetic route to the active core was developed using palladium-catalyzed Buchwald-Hartwig amination reactions of N-alkyl-O-(4-methoxybenzyl)hydroxylamines with 2-halo-pyridines that facilitated SAR studies and revealed the simplest active structural fragment. This work shows the value of using a combination of diversity-oriented synthesis (DOS) and parallel synthesis for identifying new antibacterial scaffolds.

  15. Extended Wordsearches in Chemistry

    Science.gov (United States)

    Cotton, Simon

    1998-04-01

    Students can be encouraged to develop their factual knowledge by use of puzzles. One strategy described here is the extended wordsearch, where the wordsearch element generates a number of words or phrases from which the answers to a series of questions are selected. The wordsearch can be generated with the aid of computer programs, though in order to make them suitable for students with dyslexia or other learning difficulties, a simpler form is more appropriate. These problems can be employed in a variety of contexts, for example, as topic tests and classroom end-of-lesson fillers. An example is provided in the area of calcium chemistry. Sources of suitable software are listed.

  16. Why Teach Environmental Chemistry?

    Science.gov (United States)

    Gardner, Marjorie H.

    1974-01-01

    Discusses the importance of teaching environmental chemistry in secondary school science classes, and outlines five examples of environmental chemistry problems that focus on major concepts of chemistry and have critical implications for human survival and well-being. (JR)

  17. BONDING ALUMINUM METALS

    Science.gov (United States)

    Noland, R.A.; Walker, D.E.

    1961-06-13

    A process is given for bonding aluminum to aluminum. Silicon powder is applied to at least one of the two surfaces of the two elements to be bonded, the two elements are assembled and rubbed against each other at room temperature whereby any oxide film is ruptured by the silicon crystals in the interface; thereafter heat and pressure are applied whereby an aluminum-silicon alloy is formed, squeezed out from the interface together with any oxide film, and the elements are bonded.

  18. Hydrogen peroxide coordination to cobalt(II) facilitated by second-sphere hydrogen bonding

    Czech Academy of Sciences Publication Activity Database

    Wallen, C.M.; Palatinus, Lukáš; Bacsa, J.; Scarborough, C.C.

    2016-01-01

    Roč. 55, č. 39 (2016), s. 11902-11906 ISSN 0044-8249 Institutional support: RVO:68378271 Keywords : cobalt * hydrogen bonds * peroxides * peroxido ligands * second-sphere interactions Subject RIV: CC - Organic Chemistry

  19. Environmentally Benign Sol-Gel Surface Treatment for Aluminum Bonding Applications

    National Research Council Canada - National Science Library

    Osborne, Joseph

    1996-01-01

    A surface treatment process for aluminum using sol-gel chemistry has been developed that produces strong adhesive bonds without the rinse water requirements of traditional anodizing or etching processes...

  20. Environmental chemistry. Seventh edition

    Energy Technology Data Exchange (ETDEWEB)

    Manahan, S.E. [Univ. of Missouri, Columbia, MO (United States)

    1999-11-01

    This book presents a basic understanding of environmental chemistry and its applications. In addition to providing updated materials in this field, the book emphasizes the major concepts essential to the practice of environmental chemistry. Topics of discussion include the following: toxicological chemistry; toxicological chemistry of chemical substances; chemical analysis of water and wastewater; chemical analysis of wastes and solids; air and gas analysis; chemical analysis of biological materials and xenobiotics; fundamentals of chemistry; and fundamentals of organic chemistry.

  1. Supramolecular Chemistry

    Indian Academy of Sciences (India)

    A dream target of nature inspired synthesis is to prepare 'smart' functional molecules which are so de- ... erativity, the free energy change (ΔG) is either decreased or in- .... The AIE strategy offers advantages such as high selectivity, sensitivity,.

  2. Actinide separative chemistry

    International Nuclear Information System (INIS)

    Boullis, B.

    2004-01-01

    Actinide separative chemistry has focused very heavy work during the last decades. The main was nuclear spent fuel reprocessing: solvent extraction processes appeared quickly a suitable, an efficient way to recover major actinides (uranium and plutonium), and an extensive research, concerning both process chemistry and chemical engineering technologies, allowed the industrial development in this field. We can observe for about half a century a succession of Purex plants which, if based on the same initial discovery (i.e. the outstanding properties of a molecule, the famous TBP), present huge improvements at each step, for a large part due to an increased mastery of the mechanisms involved. And actinide separation should still focus R and D in the near future: there is a real, an important need for this, even if reprocessing may appear as a mature industry. We can present three main reasons for this. First, actinide recycling appear as a key-issue for future nuclear fuel cycles, both for waste management optimization and for conservation of natural resource; and the need concerns not only major actinide but also so-called minor ones, thus enlarging the scope of the investigation. Second, extraction processes are not well mastered at microscopic scale: there is a real, great lack in fundamental knowledge, useful or even necessary for process optimization (for instance, how to design the best extracting molecule, taken into account the several notifications and constraints, from selectivity to radiolytic resistivity?); and such a need for a real optimization is to be more accurate with the search of always cheaper, cleaner processes. And then, there is room too for exploratory research, on new concepts-perhaps for processing quite new fuels- which could appear attractive and justify further developments to be properly assessed: pyro-processes first, but also others, like chemistry in 'extreme' or 'unusual' conditions (supercritical solvents, sono-chemistry, could be

  3. 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...

  4. USSR Report Chemistry

    National Research Council Canada - National Science Library

    1986-01-01

    Contents: Adsorption, Chemistry,Alkaloids, Analytical Chemistry, Catalysis,Chemical Industry,,Coal Gasification, Combustion, Electrochemistry,Explosives and Explosions, Fertilizers, Free Radicals, Inorganic...

  5. Supramolecular chemistry: from molecular information towards self-organization and complex matter

    International Nuclear Information System (INIS)

    Lehn, Jean-Marie

    2004-01-01

    Molecular chemistry has developed a wide range of very powerful procedures for constructing ever more sophisticated molecules from atoms linked by covalent bonds. Beyond molecular chemistry lies supramolecular chemistry, which aims at developing highly complex chemical systems from components interacting via non-covalent intermolecular forces. By the appropriate manipulation of these interactions, supramolecular chemistry became progressively the chemistry of molecular information, involving the storage of information at the molecular level, in the structural features, and its retrieval, transfer, and processing at the supramolecular level, through molecular recognition processes operating via specific interactional algorithms. This has paved the way towards apprehending chemistry also as an information science. Numerous receptors capable of recognizing, i.e. selectively binding, specific substrates have been developed, based on the molecular information stored in the interacting species. Suitably functionalized receptors may perform supramolecular catalysis and selective transport processes. In combination with polymolecular organization, recognition opens ways towards the design of molecular and supramolecular devices based on functional (photoactive, electroactive, ionoactive, etc) components. A step beyond preorganization consists in the design of systems undergoing self-organization, i.e. systems capable of spontaneously generating well-defined supramolecular architectures by self-assembly from their components. Self-organization processes, directed by the molecular information stored in the components and read out at the supramolecular level through specific interactions, represent the operation of programmed chemical systems. They have been implemented for the generation of a variety of discrete functional architectures of either organic or inorganic nature. Self-organization processes also give access to advanced supramolecular materials, such as

  6. On differences between hydrogen bonding and improper blue-shifting hydrogen bonding

    Czech Academy of Sciences Publication Activity Database

    Zierkiewicz, W.; Jurečka, Petr; Hobza, Pavel

    2005-01-01

    Roč. 6, č. 4 (2005), s. 609-617 ISSN 1439-4235 R&D Projects: GA ČR(CZ) GA203/05/0009; GA MŠk(CZ) LC512 Institutional research plan: CEZ:AV0Z40550506 Keywords : ab initio calculations * density functional calculations * H-bonding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.607, year: 2005

  7. 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.

  8. Water chemistry

    International Nuclear Information System (INIS)

    Hofstetter, K.J.; Baston, V.F.

    1986-01-01

    Prior to the accident, the coolants in the primary and secondary systems were within normal chemistry specifications for an operating pressurized water reactor with once-through steam generators. During and immediately after the accident, additional boric acid and sodium hydroxide were added to the primary coolant for control of criticality and radioiodine solubility. A primary to secondary leak developed contaminating the water in one steam generator. For about 5 years after the accident, the primary coolant was maintained at 3800 +. 100 ppm boron and 1000 +. 100 ppm sodium concentrations. Dissolved oxygen was maintained 7.5, corrosion caused by increased dissolved oxygen levels (up to 8 ppm) and higher chloride ion content (up to 5 ppm) is minimized. Chemical control of dissolved oxygen was discontinued and the coolant was processed. Prior to removal of the reactor vessel head, the boron concentration in the coolant was increased to ≅ 5000 ppm to support future defueling operations. Decontamination of the accident generated water is described in terms of contaminated water management. In addition, the decontamination and chemical lay-up conditions for the secondary system are presented along with an overview of chemical management at TMI-2

  9. PEROXYNITRITE CHEMISTRY

    Energy Technology Data Exchange (ETDEWEB)

    Lymar, S.V.

    2000-11-29

    This century old area of research has been experiencing a renaissance during the last decade, with the annual number of publications on the subject increasing from only one in 1990 to nearly 200 in the late-1990s. This renewed interest is stimulated by the discovery of biological roles of nitric oxide, distinguished by the 1998 Nobel prize, and the recognition that the conversion of nitric oxide into peroxynitrite may play major roles in human diseases associated with oxidative stress and in cellular defense against invading pathogens. Peroxynitrite (ONOO{sup {minus}})is a structural isomer of nitrate (NO{sub 3}{sup {minus}}) that contains a peroxo bond. The physiological route to ONOO{sup {minus}} is provided by the combination of nitric oxide ({center_dot}NO) with superoxide ({center_dot}O{sub 2}{sup {minus}}), an extremely rapid reaction occurring upon every encounter of these radicals (the upper dot denotes radical species). Both {center_dot}NO and {center_dot}O{sub 2}{sup {minus}} are the oxygen metabolic products simultaneously generated in a number of cell types within a human body. Compared to its precursors, peroxynitrite is a much stronger oxidant capable of oxidizing proteins, nucleic acids, and lipids.

  10. Introduction of a Simple Experiment for the Undergraduate Organic Chemistry Laboratory Demonstrating the Lewis Acid and Shape-Selective Properties of Zeolite Na-Y

    Science.gov (United States)

    Maloney, Vincent; Szczepanski, Zach

    2017-01-01

    A simple, inexpensive, discovery-based experiment for undergraduate organic laboratories has been developed that demonstrates the Lewis acid and shape-selective properties of zeolites. Calcined zeolite Na-Y promotes the electrophilic aromatic bromination of toluene with a significantly higher para/ortho ratio than observed under conventional…

  11. New selective and potent 5-HT1B/1D antagonists : Chemistry and pharmacological evaluation of N-piperazinylphenyl biphenylcarboxamides and biphenylsulfonamides

    NARCIS (Netherlands)

    Liao, Y; Bottcher, H; Harting, J; Greiner, H; van Amsterdam, C; Cremers, T; Sundell, S; Marz, J; Rautenberg, W; Wikstrom, H

    2000-01-01

    A series of new analogues of N-[4-methoxy-3-(4-methylpiperazin-1-yl)phenyl] 2'-methyl-4'-(5-methyl-1,2,4-oxadiazol-3-yl)biphenyl-4-carboxamide (1; GR127935) as potent and selective 5-HT1B/1D antagonists were synthesized and evaluated pharmacologically. Their receptor binding profiles were comparable

  12. 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.

  13. Cryogenic ion chemistry and spectroscopy.

    Science.gov (United States)

    Wolk, Arron B; Leavitt, Christopher M; Garand, Etienne; Johnson, Mark A

    2014-01-21

    The use of mass spectrometry in macromolecular analysis is an incredibly important technique and has allowed efficient identification of secondary and tertiary protein structures. Over 20 years ago, Chemistry Nobelist John Fenn and co-workers revolutionized mass spectrometry by developing ways to non-destructively extract large molecules directly from solution into the gas phase. This advance, in turn, enabled rapid sequencing of biopolymers through tandem mass spectrometry at the heart of the burgeoning field of proteomics. In this Account, we discuss how cryogenic cooling, mass selection, and reactive processing together provide a powerful way to characterize ion structures as well as rationally synthesize labile reaction intermediates. This is accomplished by first cooling the ions close to 10 K and condensing onto them weakly bound, chemically inert small molecules or rare gas atoms. This assembly can then be used as a medium in which to quench reactive encounters by rapid evaporation of the adducts, as well as provide a universal means for acquiring highly resolved vibrational action spectra of the embedded species by photoinduced mass loss. Moreover, the spectroscopic measurements can be obtained with readily available, broadly tunable pulsed infrared lasers because absorption of a single photon is sufficient to induce evaporation. We discuss the implementation of these methods with a new type of hybrid photofragmentation mass spectrometer involving two stages of mass selection with two laser excitation regions interfaced to the cryogenic ion source. We illustrate several capabilities of the cryogenic ion spectrometer by presenting recent applications to peptides, a biomimetic catalyst, a large antibiotic molecule (vancomycin), and reaction intermediates pertinent to the chemistry of the ionosphere. First, we demonstrate how site-specific isotopic substitution can be used to identify bands due to local functional groups in a protonated tripeptide designed to

  14. 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...

  15. Corporate Bonds in Denmark

    DEFF Research Database (Denmark)

    Tell, Michael

    2015-01-01

    Corporate financing is the choice between capital generated by the corporation and capital from external investors. However, since the financial crisis shook the markets in 2007–2008, financing opportunities through the classical means of financing have decreased. As a result, corporations have...... 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...... markets. However, NASDAQ OMX has introduced the First North Bond Market in December 2012 and new regulatory framework came into place in 2014, which may contribute to a Danish based corporate bond market. The purpose of this article is to present the regulatory changes in Denmark in relation to corporate...

  16. 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

  17. Host plant selection by a monophagous herbivore is not mediated by quantitative changes in unique plant chemistry : Agonopterix alstroemeriana and Conium maculatum

    OpenAIRE

    Castells, Eva

    2008-01-01

    Host plant selection by ovipositing females is a key process determining the success of phytophagous insects. In oligophagous lepidopterans, host-specific plant secondary chemicals are expected to be dominant factors governing oviposition behavior; distinctive compounds can serve as high-contrast signals that clearly differentiate confamilial hosts from non-hosts increasing the accuracy of host quality evaluation. Agonopterix alstroemeriana (Clerk) (Lepidoptera: Oecophoridae) and Conium macul...

  18. The Golden ratio, ionic and atomic radii and bond lengths

    Czech Academy of Sciences Publication Activity Database

    Heyrovská, Rajalakshmi

    2005-01-01

    Roč. 103, 6-8 (2005), s. 877-882 ISSN 0026-8976 R&D Projects: GA MPO(CZ) 1H-PK/42 Institutional research plan: CEZ:AV0Z40400503 Keywords : Bohr radius * bond lengths * axial ratios Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.351, year: 2005

  19. Polar Flattening and the Strength of Halogen Bonding

    Czech Academy of Sciences Publication Activity Database

    Sedlák, Robert; Kolář, Michal H.; Hobza, Pavel

    2015-01-01

    Roč. 11, č. 10 (2015), s. 4727-4732 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Institutional support: RVO:61388963 Keywords : density functional theory * interaction energies * halogen bonding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.301, year: 2015

  20. Polarization-induced sigma-holes and hydrogen bonding

    Czech Academy of Sciences Publication Activity Database

    Hennemann, M.; Murray, J. S.; Politzer, P.; Riley, Kevin Eugene; Clark, T.

    2012-01-01

    Roč. 18, č. 6 (2012), s. 2461-2469 ISSN 1610-2940 Institutional research plan: CEZ:AV0Z40550506 Keywords : hydrogen bond * sigma-hole * polarization * field effect * ab initio calculation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.984, year: 2012

  1. Bond strength of plasma sprayed ceramic coatings on phosphate steels

    Czech Academy of Sciences Publication Activity Database

    Pokorný, P.; Mastný, L.; Sýkora, V.; Pala, Zdeněk; Brožek, Vlastimil

    2015-01-01

    Roč. 54, č. 2 (2015), s. 411-414 ISSN 0543-5846 R&D Projects: GA ČR(CZ) GAP108/12/1872 Institutional support: RVO:61389021 Keywords : phosphating * plasma spraying * ceramic coatings * corrosion * bond strength Subject RIV: CA - Inorganic Chemistry Impact factor: 0.959, year: 2014

  2. Why is the Bond Multiplicity in C2 so Elusive?

    Czech Academy of Sciences Publication Activity Database

    Cooper, D.L.; Penotti, F.E.; Ponec, Robert

    2015-01-01

    Roč. 1053, SI (2015), s. 189-194 ISSN 2210-271X Institutional support: RVO:67985858 Keywords : bond multiplicity in C2 * spin correlation matrices * full GVB and spin-coupled Subject RIV: CC - Organic Chemistry Impact factor: 1.403, year: 2015

  3. 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

  4. 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

  5. Electron tunneling in chemistry

    International Nuclear Information System (INIS)

    Zamaraev, K.I.; Khajrutdinov, R.F.; Zhdanov, V.P.; Molin, Yu.N.

    1985-01-01

    Results of experimental and theoretical investigations are outlined systematically on electron tunnelling in chemical reactions. Mechanism of electron transport to great distances is shown to be characteristic to chemical compounds of a wide range. The function of tunnel reactions is discussed for various fields of chemistry, including radiation chemistry, electrochemistry, chemistry of solids, chemistry of surface and catalysis

  6. Chemistry with synchrotron radiation

    International Nuclear Information System (INIS)

    Preses, J.; Grover, J.R.; White, M.G.; Kvick, A.

    1990-01-01

    An accidental by-product of high-energy physics, synchrotron radiation, has emerged as one of the most powerful tools for the understanding of chemical reactions. Advances made by using synchrotron radiation in physical chemistry are reviewed herein. Descriptions of experiments exploiting the many ways that synchrotron radiation can be manipulated are presented. These manipulations include intensification of the radiation and compression or shifting of its spectral structure. Combinations of the use of synchrotron radiation, which provides access to very short wavelengths and is, at the same time, continuously and easily tunable, with laser radiation, which offers much higher resolution and much more intense radiation per pulse, but is difficult to tune in the ultraviolet region of the spectra, gives the chemist a way to map a molecule's potential energy curve, to note the lengths and strengths of chemical bonds, and to predict and explain novel reactions of more complex molecules. The use of diffraction of x-rays to study the spacing of atoms in crystals is discussed. Various applications of synchrotron radiation to studies of the fluorescence of hydrocarbons and to the chiral dichroism studies of other natural products like DNA and RNA are described. Methods for enhancing synchrotron light sources by insertion devices, such as wigglers and undulators, that increase the available photo flux and construction of new sources of synchrotron radiation are mentioned

  7. Molten fluoride fuel salt chemistry

    International Nuclear Information System (INIS)

    Toth, L.M.; Del Cul, G.D.; Dai, S.; Metcalf, D.H.

    1995-01-01

    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. 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 which can be used effectively to reduce the amount of development required for future systems, some significant molten salt chemical questions must still be addressed. copyright American Institute of Physics 1995

  8. Mass spectrometry in clinical chemistry

    International Nuclear Information System (INIS)

    Pettersen, J.E.

    1977-01-01

    A brief description is given of the functional elements of a mass spectrometer and of some currently employed mass spectrometric techniques, such as combined gas chromatography-mass spectrometry, mass chromatography, and selected ion monitoring. Various areas of application of mass spectrometry in clinical chemistry are discussed, such as inborn errors of metabolism and other metabolic disorders, intoxications, quantitative determinations of drugs, hormones, gases, and trace elements, and the use of isotope dilution mass spectrometry as a definitive method for the establishment of true values for concentrations of various compounds in reference sera. It is concluded that mass spectrometry is of great value in clinical chemistry. (Auth.)

  9. Photoswitchable Intramolecular Hydrogen Bonds in 5-Phenylazopyrimidines Revealed By In Situ Irradiation NMR Spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Procházková, Eliška; Čechová, Lucie; Kind, J.; Janeba, Zlatko; Thiele, C. M.; Dračínský, Martin

    2018-01-01

    Roč. 24, č. 2 (2018), s. 492-498 ISSN 0947-6539 R&D Projects: GA ČR GA15-11223S Institutional support: RVO:61388963 Keywords : azopyrimidines * heterocycles * hydrogen bonds * NMR spectroscopy * UV/Vis in situ irradiation Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 5.317, year: 2016

  10. Per-2,3-O-alkylated beta-cyclodextrin duplexes connected with disulfide bonds

    Czech Academy of Sciences Publication Activity Database

    Tatar, Ameneh; Grishina, Anastasia; Buděšínský, Miloš; Kraus, Tomáš

    2017-01-01

    Roč. 29, č. 1 (2017), s. 40-48 ISSN 1061-0278 R&D Projects: GA MŠk LD12019 Grant - others:COST(XE) CM1005 Institutional support: RVO:61388963 Keywords : cyclodextrins * inclusion complexes * disulfide bonds Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 1.264, year: 2016

  11. Representations of Chemical Bonding Models in School Textbooks--Help or Hindrance for Understanding?

    Science.gov (United States)

    Bergqvist, Anna; Drechsler, Michal; De Jong, Onno; Rundgren, Shu-Nu Chang

    2013-01-01

    Models play an important and central role in science as well as in science education. Chemical bonding is one of the most important topics in upper secondary school chemistry, and this topic is dominated by the use of models. In the past decade, research has shown that chemical bonding is a topic that students find difficult, and therefore, a wide…

  12. 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…

  13. Chemical Bond Energies of 3d Transition Metals Studied by Density Functional Theory

    DEFF Research Database (Denmark)

    Moltved, Klaus A.d; Kepp, Kasper P.

    2018-01-01

    Despite their vast importance to inorganic chemistry, materials science and catalysis, the accuracy of modelling the formation or cleavage of metal-ligand (M-L) bonds depends greatly on the chosen functional and the type of bond in a way that is not systematically understood. In order to approach...

  14. Indirect measurement of the cooperative hydrogen bonding of polymers using NMR quadrupole relaxation and PFG methods

    Czech Academy of Sciences Publication Activity Database

    Kříž, Jaroslav; Dybal, Jiří

    2008-01-01

    Roč. 265, č. 1 (2008), s. 225-232 ISSN 1022-1360. [European Symposium on Polymer Spectroscopy /17./. Seggauberg Leibnitz, 09.9.2007-12.09.2007] R&D Projects: GA AV ČR IAA400500604 Institutional research plan: CEZ:AV0Z40500505 Keywords : cooperative bonding * hydrogen bond * NMR * poly(4-vinylphenol) Subject RIV: CD - Macromolecular Chemistry

  15. 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.

  16. 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

  17. Adhesive bonding using variable frequency microwave energy

    Science.gov (United States)

    Lauf, Robert J.; McMillan, April D.; Paulauskas, Felix L.; Fathi, Zakaryae; Wei, Jianghua

    1998-01-01

    Methods of facilitating the adhesive bonding of various components with variable frequency microwave energy are disclosed. The time required to cure a polymeric adhesive is decreased by placing components to be bonded via the adhesive in a microwave heating apparatus having a multimode cavity and irradiated with microwaves of varying frequencies. Methods of uniformly heating various articles having conductive fibers disposed therein are provided. Microwave energy may be selectively oriented to enter an edge portion of an article having conductive fibers therein. An edge portion of an article having conductive fibers therein may be selectively shielded from microwave energy.

  18. Accessing Specific Peptide Recognition by Combinatorial Chemistry

    DEFF Research Database (Denmark)

    Li, Ming

    Molecular recognition is at the basis of all processes for life, and plays a central role in many biological processes, such as protein folding, the structural organization of cells and organelles, signal transduction, and the immune response. Hence, my PhD project is entitled “Accessing Specific...... Peptide Recognition by Combinatorial Chemistry”. Molecular recognition is a specific interaction between two or more molecules through noncovalent bonding, such as hydrogen bonding, metal coordination, van der Waals forces, π−π, hydrophobic, or electrostatic interactions. The association involves kinetic....... Combinatorial chemistry was invented in 1980s based on observation of functional aspects of the adaptive immune system. It was employed for drug development and optimization in conjunction with high-throughput synthesis and screening. (chapter 2) Combinatorial chemistry is able to rapidly produce many thousands...

  19. 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

  20. 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

  1. Click chemistry on the surface of PLGA-b-PEG polymeric nanoparticles: a novel targetable fluorescent imaging nanocarrier

    Energy Technology Data Exchange (ETDEWEB)

    Pucci, Andrea; Locatelli, Erica [University of Bologna, Dipartimento di Chimica Industriale ' Toso Montanari' (Italy); Ponti, Jessica; Uboldi, Chiara [Institute for Health and Consumer Protection, Joint Research Centre, Nanobiosciences Unit (Italy); Molinari, Valerio; Comes Franchini, Mauro, E-mail: mauro.comesfranchini@unibo.it [University of Bologna, Dipartimento di Chimica Industriale ' Toso Montanari' (Italy)

    2013-08-15

    In the quest for biocompatible nanocarriers for biomedical applications, a great deal of effort is put on engineering the nanocomposites surface in order to render them specific to the particular purpose. We developed biocompatible PLGA-b-PEG-based nanoparticles carrying a double functionality (i.e., carboxylic and acetylenic) able to serve as flexible highly selective grafting centers for cancer diagnosis and treatment. As a proof of concept, the nanocarrier was successfully functionalized with a tailored fluorescent molecule by means of click chemistry and with a targeting agent specific for glioblastoma multiforme via amidic bond formation.

  2. A long symmetric N· · ·H· · ·N hydrogen bond inbis(4-aminopyridinium)(1+) azide(1−): redetermination from the original data

    Czech Academy of Sciences Publication Activity Database

    Fábry, Jan

    2017-01-01

    Roč. 73, č. 9 (2017), s. 1344-1347 ISSN 2056-9890 R&D Projects: GA ČR(CZ) GA15-12653S Institutional support: RVO:68378271 Keywords : hydrogen bonding * symmetric hydrogen bonds * primary amine group Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry

  3. 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.

  4. The future of discovery chemistry: quo vadis? Academic to industrial--the maturation of medicinal chemistry to chemical biology.

    Science.gov (United States)

    Hoffmann, Torsten; Bishop, Cheryl

    2010-04-01

    At Roche, we set out to think about the future role of medicinal chemistry in drug discovery in a project involving both Roche internal stakeholders and external experts in drug discovery chemistry. To derive a coherent strategy, selected scientists were asked to take extreme positions and to derive two orthogonal strategic options: chemistry as the traditional mainstream science and chemistry as the central entrepreneurial science. We believe today's role of medicinal chemistry in industry has remained too narrow. To provide the innovation that industry requires, medicinal chemistry must play its part and diversify at pace with our increasing understanding of chemical biology and network pharmacology. 2010 Elsevier Ltd. All rights reserved.

  5. Contribution from philosophy of chemistry to chemistry education: In a case of ionic liquids as technochemistry

    Science.gov (United States)

    Mudzakir, Ahmad; Hernani, Widhiyanti, Tuszie; Sudrajat, Devi Pratiwi

    2017-08-01

    Traditional chemistry education is commonly handing down of concepts, principles, and theories, such as mechanical properties, the relationship between structure and properties as well as chemical structure and chemical bonding theory, to students without engaging them in the processes of chemical inquiry. This practice leads to the lack of opportunity for the students to construct an appropriate understanding of these concepts, principles, and theories. Students are also rarely facilitated in modeling the structure and function of matter themselves. This situation shows that the philosophy of chemistry has not received as much attention from chemistry educators. The main idea of this paper is to embed philosophy of chemistry through the implementation of technochemistry in chemistry education. One of the most interesting and rapidly developing areas of modern chemistry, technologies and engineering is Ionic Liquids (ILs) as an emerging knowledge on technochemistry which can be applied to chemistry education. The developments between academic researchers and industrial developments in the ILs area are conducted in parallel. In order to overcome the existing problems of scientific development in chemistry education, the science and technology of ILs can be used for reconceptualizing the teaching and learning of chemistry to embrace the epistemology in chemistry. This study promises a potential contribution by philosophy of chemistry. The main objectives of this study are to develop: (i) a perspective based on philosophy of science considerations (rational reconstruction) in order to understand ionic liquids and (ii) teaching materials that can be used to enhance pre-service teacher's view of nature of science and technology (VNOST). The method used in the study is analytical-descriptive (elementarization), i.e. the first step in the model of educational reconstruction (MER). This study concludes that the development of the concepts and their applications of ionic

  6. 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.

  7. 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...

  8. Bond markets in Africa

    Directory of Open Access Journals (Sweden)

    Yibin Mu

    2013-07-01

    Full Text Available African bond markets have been steadily growing in recent years, but nonetheless remain undeveloped. African countries would benefit from greater access to financing and deeper financial markets. This paper compiles a unique set of data on government securities and corporate bond markets in Africa. It then applies an econometric model to analyze the key determinants of African government securities market and corporate bond market capitalization. Government securities market capitalization is directly related to better institutions and interest rate volatility, and inversely related to smaller fiscal deficits, higher interest rate spreads, exchange rate volatility, and current and capital account openness. Corporate bond market capitalization is directly linked to economic size, the level of development of the economy and financial markets, better institutions, and interest rate volatility, and inversely related to higher interest rate spreads and current account openness. Policy implications follow.

  9. From hot atom chemistry to epithermal chemistry

    International Nuclear Information System (INIS)

    Roessler, K.

    2004-01-01

    The rise and fall of hot atom chemistry (HAC) over the years from 1934 to 2004 is reviewed. Several applications are discussed, in particular to astrophysics and the interaction of energetic ions and atoms in space. Epithermal chemistry (ETC) is proposed to substitute the old name, since it better fits the energy range as well as the non-thermal and non-equilibrium character of the reactions. ETC also avoids the strong connexion of HAC to nuclear chemistry and stands for the opening of the field to physical chemistry and astrophysics. (orig.)

  10. Conversion of Amides to Esters by the Nickel-Catalyzed Activation of Amide C–N Bonds

    Science.gov (United States)

    Hie, Liana; Fine Nathel, Noah F.; Shah, Tejas K.; Baker, Emma L.; Hong, Xin; Yang, Yun-Fang; Liu, Peng; Houk, K. N.; Garg, Neil K.

    2015-01-01

    Amides are common functional groups that have been well studied for more than a century.1 They serve as the key building blocks of proteins and are present in an broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to resonance stability of the amide bond.1,2 Whereas Nature can easily cleave amides through the action of enzymes, such as proteases,3 the ability to selectively break the C–N bond of an amide using synthetic chemistry is quite difficult. In this manuscript, we demonstrate that amide C–N bonds can be activated and cleaved using nickel catalysts. We have used this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory (DFT) calculations provide insight into the thermodynamics and catalytic cycle of this unusual transformation. Our results provide a new strategy to harness amide functional groups as synthons and are expected fuel the further use of amides for the construction of carbon–heteroatom or carbon–carbon bonds using non-precious metal catalysis. PMID:26200342

  11. Conversion of amides to esters by the nickel-catalysed activation of amide C-N bonds.

    Science.gov (United States)

    Hie, Liana; Fine Nathel, Noah F; Shah, Tejas K; Baker, Emma L; Hong, Xin; Yang, Yun-Fang; Liu, Peng; Houk, K N; Garg, Neil K

    2015-08-06

    Amides are common functional groups that have been studied for more than a century. They are the key building blocks of proteins and are present in a broad range of other natural and synthetic compounds. Amides are known to be poor electrophiles, which is typically attributed to the resonance stability of the amide bond. Although amides can readily be cleaved by enzymes such as proteases, it is difficult to selectively break the carbon-nitrogen bond of an amide using synthetic chemistry. Here we demonstrate that amide carbon-nitrogen bonds can be activated and cleaved using nickel catalysts. We use this methodology to convert amides to esters, which is a challenging and underdeveloped transformation. The reaction methodology proceeds under exceptionally mild reaction conditions, and avoids the use of a large excess of an alcohol nucleophile. Density functional theory calculations provide insight into the thermodynamics and catalytic cycle of the amide-to-ester transformation. Our results provide a way to harness amide functional groups as synthetic building blocks and are expected to lead to the further use of amides in the construction of carbon-heteroatom or carbon-carbon bonds using non-precious-metal catalysis.

  12. 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.

  13. Diffusion bonding techniques

    International Nuclear Information System (INIS)

    Peters, R.D.

    1978-01-01

    The applications of diffusion bonding at the General Electric Neutron Devices Department are briefly discussed, with particular emphasis on the gold/gold or gold/indium joints made between metallized alumina ceramic parts in the vacuum switch tube and the crystal resonator programs. Fixtures which use the differential expansion of dissimilar metals are described and compared to one that uses hydraulic pressure to apply the necessary bonding force

  14. Improving chemistry performance in CANDU plants

    International Nuclear Information System (INIS)

    Turner, C.; Guzonas, D.

    2010-01-01

    There is a strong interplay between coolant chemistry and materials selection in any nuclear power plant system. To achieve the design life of reactor components it is necessary to monitor and control relevant chemistry parameters, such as ionic conductivity, pH, concentrations of dissolved ions and redox species (e.g., hydrogen, hydrazine, oxygen) and the concentrations of suspended corrosion products. Chemistry specifications are set to achieve a balance between the sometimes conflicting requirements to minimize corrosion and radiological dose and to minimize operating and maintenance costs over the lifetime of the plant. For the past decade, Atomic Energy of Canada Limited (AECL) has taken a rigorous and disciplined approach to reviewing and updating all aspects of chemistry control in the CANDU® nuclear power plant (NPP). This approach has included proactively reviewing chemistry operating experience from existing CANDU® and other water-cooled NPPs worldwide to identify and address emerging issues, updating all of our chemistry control documentation to ensure that each chemistry parameter is linked to a specific requirement (e.g., reduce activity transport, monitor for condenser leak) and incorporating the latest results from our Research and Development (R and D) programs to ensure that all chemistry specifications are supported by a sound rationale. The results of this review and update have been incorporated into updated chemistry specifications and, in some cases, modified operating procedures for new and existing plants. In addition, recommendations have been made for design modifications to improve chemistry control in new build plants, especially during periods of shutdown and startup when chemistry control has traditionally been more challenging. Chemistry control in new-build CANDU® plants will rely increasingly on the use of on-line instrumentation interfaced directly to AECL's state-of-the-art chemistry monitoring, diagnostics and analysis

  15. The latest general chemistry

    International Nuclear Information System (INIS)

    Ryu, Geun Bae; Choi, Se Yeong; Kim, Chin Yeong; Yoon, Gil Jung; Lee, Eun Seok; Seo, Moon Gyu

    1995-02-01

    This book deals with the latest general chemistry, which is comprised of twenty-three chapters, the contents of this book are introduction, theory of atoms and molecule, chemical formula and a chemical reaction formula, structure of atoms, nature of atoms and the periodic table, structure of molecule and spectrum, gas, solution, solid, chemical combination, chemical reaction speed, chemical equilibrium, thermal chemistry, oxidation-reduction, electrochemistry, acid-base, complex, aquatic chemistry, air chemistry, nuclear chemistry, metal and nonmetal, organic chemistry and biochemistry. It has exercise in the end of each chapter.

  16. T. thermophila group I introns that cleave amide bonds

    Science.gov (United States)

    Joyce, Gerald F. (Inventor)

    1997-01-01

    The present invention relates to nucleic acid enzymes or enzymatic RNA molecules that are capable of cleaving a variety of bonds, including phosphodiester bonds and amide bonds, in a variety of substrates. Thus, the disclosed enzymatic RNA molecules are capable of functioning as nucleases and/or peptidases. The present invention also relates to compositions containing the disclosed enzymatic RNA molecule and to methods of making, selecting, and using such enzymes and compositions.

  17. A systematic structural study of halogen bonding versus hydrogen bonding within competitive supramolecular systems

    Directory of Open Access Journals (Sweden)

    Christer B. Aakeröy

    2015-09-01

    Full Text Available As halogen bonds gain prevalence in supramolecular synthesis and materials chemistry, it has become necessary to examine more closely how such interactions compete with or complement hydrogen bonds whenever both are present within the same system. As hydrogen and halogen bonds have several fundamental features in common, it is often difficult to predict which will be the primary interaction in a supramolecular system, especially as they have comparable strength and geometric requirements. To address this challenge, a series of molecules containing both hydrogen- and halogen-bond donors were co-crystallized with various monotopic, ditopic symmetric and ditopic asymmetric acceptor molecules. The outcome of each reaction was examined using IR spectroscopy and, whenever possible, single-crystal X-ray diffraction. 24 crystal structures were obtained and subsequently analyzed, and the synthon preferences of the competing hydrogen- and halogen-bond donors were rationalized against a background of calculated molecular electrostatic potential values. It has been shown that readily accessible electrostatic potentials can offer useful practical guidelines for predicting the most likely primary synthons in these co-crystals as long as the potential differences are weighted appropriately.

  18. 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...

  19. Bibliographies on radiation chemistry

    International Nuclear Information System (INIS)

    Greenstock, C.L.; Ross, A.B.; Helman, W.P.

    1981-01-01

    This bibliography lists about 400 papers dealing solely with the production and reactivity of superoxide radical anions in irradiated aqueous and organic liquids. Only papers dealing with quantitative mechanistic, spectroscopic or kinetic data have been included. The listing was prepared by searching the RCDC bibliographic data base with SELECT keywords O 2 - or HO 2 and aqueous solution. The key words radicals (oxygen), peroxy radicals, pulse radiolysis, flash radiolysis, esr and gamma rays were also used. Additional relevant references were obtained from inspection of reviews, individual author indexes and cited references. The present bibliography excludes solid and gas phase studies, and also technical, government and in-house reports, theses, patents and some symposia proceedings. Several references prior to 1960 have been added, and the list should be reasonably comprehensive from 1965-1980. The listing is in chronological order, according to year of publication in the categories Photochemistry, Radiation Chemistry, Other, and Reviews. (author)

  20. Nuclear chemistry

    International Nuclear Information System (INIS)

    Anon.

    1979-01-01

    Topics covered include: mass asymmetry and total kinetic energy release in the spontaneous fission of 262 105; 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 84 Kr ions in nickel, aluminium and titanium; differences in compound nuclei formed with 40 Ar and 84 Kr 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 164 Yb; contrasting behavior of h/sub 9/2/ and i/sub 13/2/ bands in 185 Au; multiple band crossings in 164 Er; recoil-distance measurement of lifetimes of rotational states in 164 Dy, lifetimes of ground-band states in 192 Pt and 194 Pt 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 32 S; 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

  1. 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, D. Kirk; 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

  2. Halonium Ions as Halogen Bond Donors in the Solid State [XL2]Y Complexes.

    Science.gov (United States)

    Rissanen, Kari; Haukka, Matti

    2015-01-01

    The utilization of halogen bonding interactions is one of the most rapidly developing areas of supramolecular chemistry. While the other weak non-covalent interactions and their influence on the structure and chemistry of various molecules, complexes, and materials have been investigated extensively, the understanding, utilizations, and true nature of halogen bonding are still relatively unexplored. Thus its final impact in chemistry in general and in materials science has not yet been fully established. Because of the polarized nature of a Z-X bond (Z=electron-withdrawing atom or moiety and X=halogen atom), such a moiety can act as halogen bond donor when the halogen is polarized enough by the atom/moiety Z. The most studied and utilized halogen bond donor molecules are the perfluorohalocarbons, where Z is a perfluorinated aryl or alkyl moiety and X is either iodine or bromine. Complementing the contemporary halogen bonding research, this chapter reviews the solid state structural chemistry of the most extremely polarized halogen atoms, viz. halonium ions, X+, and discussed them as halogen bond donors in the solid state [XL2]Y complexes (X=halonium ion, Y=any anion).

  3. 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.

  4. Advanced Chemistry Laboratory

    Data.gov (United States)

    Federal Laboratory Consortium — Description/History: Chemistry laboratoryThe Advanced Chemistry Laboratory (ACL) is a unique facility designed for working with the most super toxic compounds known...

  5. 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.

  6. Interstellar hydrogen bonding

    Science.gov (United States)

    Etim, Emmanuel E.; Gorai, Prasanta; Das, Ankan; Chakrabarti, Sandip K.; Arunan, Elangannan

    2018-06-01

    This paper reports the first extensive study of the existence and effects of interstellar hydrogen bonding. The reactions that occur on the surface of the interstellar dust grains are the dominant processes by which interstellar molecules are formed. Water molecules constitute about 70% of the interstellar ice. These water molecules serve as the platform for hydrogen bonding. High level quantum chemical simulations for the hydrogen bond interaction between 20 interstellar molecules (known and possible) and water are carried out using different ab-intio methods. It is evident that if the formation of these species is mainly governed by the ice phase reactions, there is a direct correlation between the binding energies of these complexes and the gas phase abundances of these interstellar molecules. Interstellar hydrogen bonding may cause lower gas abundance of the complex organic molecules (COMs) at the low temperature. From these results, ketenes whose less stable isomers that are more strongly bonded to the surface of the interstellar dust grains have been observed are proposed as suitable candidates for astronomical observations.

  7. Metal-mediated DNA base pairing: alternatives to hydrogen-bonded Watson-Crick base pairs.

    Science.gov (United States)

    Takezawa, Yusuke; Shionoya, Mitsuhiko

    2012-12-18

    With its capacity to store and transfer the genetic information within a sequence of monomers, DNA forms its central role in chemical evolution through replication and amplification. This elegant behavior is largely based on highly specific molecular recognition between nucleobases through the specific hydrogen bonds in the Watson-Crick base pairing system. While the native base pairs have been amazingly sophisticated through the long history of evolution, synthetic chemists have devoted considerable efforts to create alternative base pairing systems in recent decades. Most of these new systems were designed based on the shape complementarity of the pairs or the rearrangement of hydrogen-bonding patterns. We wondered whether metal coordination could serve as an alternative driving force for DNA base pairing and why hydrogen bonding was selected on Earth in the course of molecular evolution. Therefore, we envisioned an alternative design strategy: we replaced hydrogen bonding with another important scheme in biological systems, metal-coordination bonding. In this Account, we provide an overview of the chemistry of metal-mediated base pairing including basic concepts, molecular design, characteristic structures and properties, and possible applications of DNA-based molecular systems. We describe several examples of artificial metal-mediated base pairs, such as Cu(2+)-mediated hydroxypyridone base pair, H-Cu(2+)-H (where H denotes a hydroxypyridone-bearing nucleoside), developed by us and other researchers. To design the metallo-base pairs we carefully chose appropriate combinations of ligand-bearing nucleosides and metal ions. As expected from their stronger bonding through metal coordination, DNA duplexes possessing metallo-base pairs exhibited higher thermal stability than natural hydrogen-bonded DNAs. Furthermore, we could also use metal-mediated base pairs to construct or induce other high-order structures. These features could lead to metal-responsive functional

  8. Safe and Liquid Mortgage Bonds

    DEFF Research Database (Denmark)

    Dick-Nielsen, Jens; Gyntelberg, Jacob; Lund, Jesper

    This paper shows that strict match pass-through funding of covered bonds provides safe and liquid mortgage bonds. Despite a 30% drop in house prices during the 2008 global crisis Danish mortgage bonds remained as liquid as most European government bonds. The Danish pass-through system effectively...... eliminates credit risk from the investor's perspective. Similar to other safe bonds, funding liquidity becomes the main driver of mortgage bond liquidity and this creates commonality in liquidity across markets and countries. These findings have implications for how to design a robust mortgage bond system...

  9. Sulfate Recognition by Persistent Crystalline Capsules with Rigidified Hydrogen Bonding Cavities

    International Nuclear Information System (INIS)

    Custelcean, Radu; Remy, Priscilla; Jiang, Deen; Bonnesen, Peter V; Moyer, Bruce A

    2008-01-01

    electivity is a fundamental property of pervasive importance in chemistry and biology as reflected in phenomena as diverse as membrane transport, catalysis, sensing, adsorption, complexation, and crystallization. Although the key principles of complementarity and preorganization governing the binding interactions underlying such phenomena were delineated long ago, truly profound selectivity has proven elusive by design in part because synthetic molecular architectures are neither maximally complementary for binding target species nor sufficiently rigid. Even if a host molecule possesses a high degree of complementarity for a guest species, it all too often can distort its structure or even rearrange its conformation altogether to accommodate competing guests. One approach taken by researchers to overcome this challenge has been to devise extremely rigid molecules that bind species within complementary cavities. Although examples have been reported to demonstrate the principle, such cases are not generally of practical utility, because of inefficient synthesis and often poor kinetics. Alternatively, flexible building blocks can be employed, but then the challenge becomes one of locking them in place. Taking a cue from natural binding agents that derive their rigidity from a network of molecular interactions, especially hydrogen bonding, we present herein an example of a crystalline, self-assembled capsule that binds sulfate by a highly complementary array of rigidified hydrogen bonds (H-bonds). Although covalent or self-assembled capsules have been previously employed as anion hosts, they typically lack the strict combination of complementarity and rigidity required for high selectivity. Furthermore, the available structural data for these systems is either restricted to a limited number of anions of similar size and shape, or varies significantly from one anion to another, which hampers the rationalization of the observed selectivity. We have been employing

  10. Preparative radiation chemistry

    International Nuclear Information System (INIS)

    Drawe, H.

    1978-01-01

    Preparative synthesis of compounds with the aid of radiation chemistry is increasingly used in laboratories as well as on a technical scale. A large number of new compounds has been produced with the methods of radiation chemistry. With the increasing number of available radiation sources, also the number of synthesis metods in radiation chemistry has increased. This paper can only briefly mention the many possible ways of synthesis in radiation chemistry. (orig./HK) [de

  11. USSR Report Chemistry

    National Research Council Canada - National Science Library

    1986-01-01

    THIS REPORT CONTAINS FOREIGN MEDIA INFORMATION FROM THE USSR CONCERNING Adsorption, Alkaloids, ANALYTICAL CHEMISTRY, CATALYSIS, ELECTROCHEMISTRY, Fertilizers, INORGANIC COMPOUNDS, ORGANOPHOSPHOROUS...

  12. Analytical chemistry instrumentation

    International Nuclear Information System (INIS)

    Laing, W.R.

    1986-01-01

    In nine sections, 48 chapters cover 1) analytical chemistry and the environment 2) environmental radiochemistry 3) automated instrumentation 4) advances in analytical mass spectrometry 5) fourier transform spectroscopy 6) analytical chemistry of plutonium 7) nuclear analytical chemistry 8) chemometrics and 9) nuclear fuel technology

  13. Fundamentals of nuclear chemistry

    International Nuclear Information System (INIS)

    Majer, V.

    1982-01-01

    The author of the book has had 25 years of experience at the Nuclear Chemistry of Prague Technical University. In consequence, the book is intended as a basic textbook for students of this field. Its main objectives are an easily understandable presentation of the complex subject and in spite of the uncertainty which still characterizes the definition and subjects of nuclear chemistry - a systematic classification and logical structure. Contents: 1. Introduction (history and definition); 2. General nuclear chemistry (physical fundamentals, hot atom chemistry, interaction of nuclear radiation with matter, radioactive elements, isotope effects, isotope exchange, chemistry of radioactive trace elements); 3. Methods of nuclear chemistry of nuclear chemistry (radiochemical methods, activation, separation and enrichment chemistry); 4. Preparative nuclear chemistry (isotope production, labelled compounds); 5. Analytival nuclear chemistry; 6. Applied nuclear chemistry (isotope applications in general physical and analytical chemistry). The book is supplemented by an annex with tables, a name catalogue and a subject index which will facilitate access to important information. (RB) [de

  14. Contribution of microreactor technology and flow chemistry to the development of green and sustainable synthesis

    Directory of Open Access Journals (Sweden)

    Flavio Fanelli

    2017-03-01

    Full Text Available Microreactor technology and flow chemistry could play an important role in the development of green and sustainable synthetic processes. In this review, some recent relevant examples in the field of flash chemistry, catalysis, hazardous chemistry and continuous flow processing are described. Selected examples highlight the role that flow chemistry could play in the near future for a sustainable development.

  15. Contribution of microreactor technology and flow chemistry to the development of green and sustainable synthesis.

    Science.gov (United States)

    Fanelli, Flavio; Parisi, Giovanna; Degennaro, Leonardo; Luisi, Renzo

    2017-01-01

    Microreactor technology and flow chemistry could play an important role in the development of green and sustainable synthetic processes. In this review, some recent relevant examples in the field of flash chemistry, catalysis, hazardous chemistry and continuous flow processing are described. Selected examples highlight the role that flow chemistry could play in the near future for a sustainable development.

  16. Potential application of palladium nanoparticles as selective recyclable hydrogenation catalysts

    International Nuclear Information System (INIS)

    Mukherjee, DebKumar

    2008-01-01

    The search for more efficient catalytic systems that might combine the advantages of both homogeneous (catalyst modulation) and heterogeneous (catalyst recycling) catalysis is one of the most exciting challenges of modern chemistry. More recently with the advances of nanochemistry, it has been possible to prepare soluble analogues of heterogeneous catalysts. These nanoparticles are generally stabilized against aggregation into larger particles by electrostatic or steric protection. Herein we demonstrate the use of room temperature ionic liquid for the stabilization of palladium nanoparticles that are recyclable catalysts for the hydrogenation of carbon-carbon double bonds and application of these catalysts to the selective hydrogenation of internal or terminal C=C bonds in unsaturated primary alcohols. The particles suspended in room temperature ionic liquid show no metal aggregation or loss of catalytic activity even on prolonged use

  17. American Association for Clinical Chemistry

    Science.gov (United States)

    ... Find the answer to your question IN CLINICAL CHEMISTRY Hs-cTnI as a Gatekeeper for Further Cardiac ... Online Harmonization.net Commission on Accreditation in Clinical Chemistry American Board of Clinical Chemistry Clinical Chemistry Trainee ...

  18. Hydrogen bonded supramolecular materials

    CERN Document Server

    Li, Zhan-Ting

    2015-01-01

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

  19. Continuing bonds and place.

    Science.gov (United States)

    Jonsson, Annika; Walter, Tony

    2017-08-01

    Where do people feel closest to those they have lost? This article explores how continuing bonds with a deceased person can be rooted in a particular place or places. Some conceptual resources are sketched, namely continuing bonds, place attachment, ancestral places, home, reminder theory, and loss of place. The authors use these concepts to analyze interview material with seven Swedes and five Britons who often thought warmly of the deceased as residing in a particular place and often performing characteristic actions. The destruction of such a place, by contrast, could create a troubling, haunting absence, complicating the deceased's absent-presence.

  20. Electrolyte chemistry control in electrodialysis processing

    Science.gov (United States)

    Hayes, Thomas D.; Severin, Blaine F.

    2017-12-26

    Methods for controlling electrolyte chemistry in electrodialysis units having an anode and a cathode each in an electrolyte of a selected concentration and a membrane stack disposed therebetween. The membrane stack includes pairs of cationic selective and anionic membranes to segregate increasingly dilute salts streams from concentrated salts stream. Electrolyte chemistry control is via use of at least one of following techniques: a single calcium exclusionary cationic selective membrane at a cathode cell boundary, an exclusionary membrane configured as a hydraulically isolated scavenger cell, a multivalent scavenger co-electrolyte and combinations thereof.

  1. Iridium complexes containing mesoionic C donors: selective C(sp3)-H versus C(sp2)-H bond activation, reactivity towards acids and bases, and catalytic oxidation of silanes and water.

    Science.gov (United States)

    Petronilho, Ana; Woods, James A; Mueller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

    2014-11-24

    Metalation of a C2-methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp(3))-H bond activation of the C2-bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp(2))-H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp(2))-H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D(+) and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir-C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6,000 h(-1) with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol-4-ylidene ligands and is more than three times faster than with the triazolylidene analogue. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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.

  3. Metal-composite adhesion based on diazonium chemistry.

    Science.gov (United States)

    Oweis, Yara; Alageel, Omar; Kozak, Paige; Abdallah, Mohamed-Nur; Retrouvey, Jean-Marc; Cerruti, Marta; Tamimi, Faleh

    2017-11-01

    Composite resins do not adhere well to dental alloys. This weak bond can result in failure at the composite-metal interface in fixed dental prostheses and orthodontic brackets. The aim of this study was to develop a new adhesive, based on diazonium chemistry, to facilitate chemical bonding between dental alloys and composite resin. Samples of two types of dental alloys, stainless steel and cobalt chromium were primed with a diazonium layer in order to create a surface coating favorable for composite adhesion. Untreated metal samples served as controls. The surface chemical composition of the treated and untreated samples was analyzed by X-ray photoelectron spectroscopy (XPS) and the tensile strength of the bond with composite resin was measured. The diazonium adhesive was also tested for shear bond strength between stainless steel orthodontic brackets and teeth. XPS confirmed the presence of a diazonium coating on the treated metals. The coating significantly increased the tensile and shear bond strengths by three and four folds respectively between the treated alloys and composite resin. diazonium chemistry can be used to develop composite adhesives for dental alloys. Diazonium adhesion can effectively achieve a strong chemical bond between dental alloys and composite resin. This technology can be used for composite repair of fractured crowns, for crown cementation with resin based cements, and for bracket bonding. Copyright © 2017 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

  4. Organofluorine chemistry: synthesis and conformation of vicinal fluoromethylene motifs.

    Science.gov (United States)

    O'Hagan, David

    2012-04-20

    The C-F bond is the most polar bond in organic chemistry, and thus the bond has a relatively large dipole moment with a significant -ve charge density on the fluorine atom and correspondingly a +ve charge density on carbon. The electrostatic nature of the bond renders it the strongest one in organic chemistry. However, the fluorine atom itself is nonpolarizable, and thus, despite the charge localization on fluorine, it is a poor hydrogen-bonding acceptor. These properties of the C-F bond make it attractive in the design of nonviscous but polar organic compounds, with a polarity limited to influencing the intramolecular nature of the molecule and less so intermolecular interactions with the immediate environment. In this Perspective, the synthesis of aliphatic chains carrying multivicinal fluoromethylene motifs is described. It emerges that the dipoles of adjacent C-F bonds orientate relative to each other, and thus, individual diastereoisomers display different backbone carbon chain conformations. These conformational preferences recognize the influence of the well-known gauche effect associated with 1,2-difluoroethane but extend to considering 1,3-fluorine-fluorine dipolar repulsions. The synthesis of carbon chains carrying two, three, four, five, and six vicinal fluoromethylene motifs is described, with an emphasis on our own research contributions. These motifs obey almost predictable conformational behavior, and they emerge as candidates for inclusion in the design of performance organic molecules. © 2012 American Chemical Society

  5. 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

  6. Fundamentals of reactor chemistry

    International Nuclear Information System (INIS)

    Akatsu, Eiko

    1981-12-01

    In the Nuclear Engineering School of JAERI, many courses are presented for the people working in and around the nuclear reactors. The curricula of the courses contain also the subject material of chemistry. With reference to the foreign curricula, a plan of educational subject material of chemistry in the Nuclear Engineering School of JAERI was considered, and the fundamental part of reactor chemistry was reviewed in this report. Since the students of the Nuclear Engineering School are not chemists, the knowledge necessary in and around the nuclear reactors was emphasized in order to familiarize the students with the reactor chemistry. The teaching experience of the fundamentals of reactor chemistry is also given. (author)

  7. Metal-Free Approaches to Sterically-Hindered Bonds

    Science.gov (United States)

    Dunham, Veronica Vin-yi

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

  8. 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.

  9. A Protein Data Bank survey reveals shortening of intermolecular hydrogen bonds in ligand-protein complexes when a halogenated ligand is an H-bond donor.

    Science.gov (United States)

    Poznański, Jarosław; Poznańska, Anna; Shugar, David

    2014-01-01

    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.

  10. Radiation chemistry in Taiwan, fundamental and applied

    International Nuclear Information System (INIS)

    Wang, U.P.

    1980-01-01

    Both fundamental and applied research works on radiation chemistry in Taiwan have been described from the view point of economic development of new radiation chemical industry by applying unique chemical reactions on radiation processing. Seven items on the basic and applied research works and the status of recent industrial development of radiation chemistry have been consequently selected to be delineated as the major contents along this line in this paper. (author)

  11. 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.

  12. Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

    Directory of Open Access Journals (Sweden)

    Peter I. Nagy

    2014-10-01

    Full Text Available A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011 or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic in acid-base complexes have been surveyed.

  13. The influence of adherent surface preparation on bond durability

    International Nuclear Information System (INIS)

    Rider, A.N.; Arnott, D.R.; Olsson-Jacques, C.L.

    1999-01-01

    Full text: One of the major factors limiting the use of adhesive bonding is the problem associated with the production of adhesive joints that can maintain their initial strength over long periods of time in hostile environments. It is well known that the adherent surface preparation method is critical to the formation of a durable adhesive bond. Work presented in this paper focuses on the critical aspects of the surface preparation of aluminium employed for the manufacture of aluminium-epoxy joints. The surface preparation procedure examined is currently employed by the RAAF for repairs requiring metal to adhesive bonding. The influence of each step in the surface preparation on the ultimate bond durability performance of the adhesive joint is examined by a combination of methods. Double cantilever wedge style adhesive joints are loaded in mode 1 opening and then exposed to a humid environment. X-ray photoelectron spectroscopy (XPS) and contact angle measurements of the aluminium adherent before bonding provides information about the adherent surface chemistry. XPS is also employed to analyse the surfaces of the bonded specimens post failure to establish the locus of fracture. This approach provides important information regarding the properties influencing bond durability as well as the bond failure mechanisms. A two step bond degradation model was developed to qualitatively describe the observed bond durability performance and fracture data. The first step involves controlled moisture ingress by stress induced microporosity of the adhesive in the interfacial region. The second step determines the locus of fracture through the relative dominance of one of three competitive processes, viz: oxide degradation, polymer desorption, or polymer degradation. A key element of the model is the control exercised over the interfacial microporosity by the combined interaction of stress and the relative densities of strong and weak linkages at the metal to adhesive interface

  14. “Impact of RACM2, halogen chemistry, and updated ozonedeposition velocity on hemispheric ozone predictions”

    Science.gov (United States)

    We incorporate the Regional Atmospheric Chemistry Mechanism (RACM2) into the Community Multiscale Air Quality (CMAQ) hemispheric model and compare model predictions to those obtained using the existing Carbon Bond chemical mechanism with updated toluene chemistry (CB05TU). The RA...

  15. Impact of RACM2, halogen chemistry, and updated ozone deposition velocity onhemispheric ozone predictions

    Science.gov (United States)

    We incorporate the Regional Atmospheric Chemistry Mechanism (RACM2) into the Community Multiscale Air Quality (CMAQ) hemispheric model and compare model predictions to those obtained using the existing Carbon Bond chemical mechanism with the updated toluene chemistry (CB05TU). Th...

  16. Solid state chemistry of new polysulphides in A/Sn/S (A = Na, K, Rb ...

    Indian Academy of Sciences (India)

    Administrator

    Solid state chemistry of new polysulphides in A/Sn/S (A = Na, K,. Rb) systems. M SUSEELA DEVI and K VIDYASAGAR. Department of Chemistry, Indian Institute of Technology Madras,. Chennai 600 036, India. Ternary polychalcogenides containing chalocogen–chalcogen bonds are metastable compounds that have been ...

  17. Comparing Amide-Forming Reactions Using Green Chemistry Metrics in an Undergraduate Organic Laboratory

    Science.gov (United States)

    Fennie, Michael W.; Roth, Jessica M.

    2016-01-01

    In this laboratory experiment, upper-division undergraduate chemistry and biochemistry majors investigate amide-bond-forming reactions from a green chemistry perspective. Using hydrocinnamic acid and benzylamine as reactants, students perform three types of amide-forming reactions: an acid chloride derivative route; a coupling reagent promoted…

  18. Annual report 1985 Chemistry Department

    International Nuclear Information System (INIS)

    Funck, J.; Larsen, E.; Nielsen, O.J.

    1986-03-01

    This report contains a brief survey of the main activities in the Chemistry Department. All particles and reports published and lectures given in 1985 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)

  19. Annual report 1984 Chemistry Department

    International Nuclear Information System (INIS)

    Funck, J.; Larsen, E.; Nielsen, O.J.

    1985-03-01

    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)

  20. Fundamentals of nuclear chemistry

    International Nuclear Information System (INIS)

    Matel, L.; Dulanska, S.

    2013-01-01

    This text-book is an introductory text in nuclear chemistry and radiochemistry, aimed on university undergraduate students in chemistry and related disciplines (physics, nuclear engineering). It covers the key aspects of modern nuclear chemistry. The text begins with basic theories in contemporary physics. It relates nuclear phenomena to key divisions of chemistry such as atomic structure, spectroscopy, equilibria and kinetics. It also gives an introduction to sources of ionizing radiation, detection of ionizing radiation, nuclear power industry and accident on nuclear installations as well as basic knowledge's of radiobiology. This book is essential reading for those taking a first course in nuclear chemistry and is a useful companion to other volumes in physical and analytical chemistry. It will also be of use to those new to working in nuclear chemistry or radiochemistry.

  1. Liquid phase solvent bonding of plastic microfluidic devices assisted by retention grooves.

    Science.gov (United States)

    Wan, Alwin M D; Sadri, Amir; Young, Edmond W K

    2015-01-01

    We report a novel method for achieving consistent liquid phase solvent bonding of plastic microfluidic devices via the use of retention grooves at the bonding interface. The grooves are patterned during the regular microfabrication process, and can be placed at the periphery of a device, or surrounding microfluidic features with open ports, where they effectively mitigate solvent evaporation, and thus substantially reduce poor bond coverage. This method is broadly applicable to a variety of plastics and solvents, and produces devices with high bond quality (i.e., coverage, strength, and microfeature fidelity) that are suitable for studies in physics, chemistry, and cell biology at the microscale.

  2. Surface chemistry of selected lunar regions

    International Nuclear Information System (INIS)

    Bielefeld, M.J.; Reedy, R.C.; Metzger, A.E.; Trombka, J.I.; Arnold, J.R.

    1976-01-01

    A completely new analysis has been carried out on the data from the Apollo 15 and 16 γ ray spectrometer experiments. The components of the continuum background have been estimated. The elements Th, K, Fe and Mg give useful results; results for Ti are significant only for a few high Ti regions. Errors are given, and the results are checked by other methods. Concentrations are reported for about sixty lunar regions; the ground track has been subdivided in various ways. The borders of the maria seem well-defined chemically, while the distribution of KREEP is broad. This wide distribution requires emplacement of KREEP before the era of mare formation. Its high concentration in western mare soils seems to require major vertical mixing

  3. Nuclear chemistry in the traditional chemistry program

    International Nuclear Information System (INIS)

    Kleppinger, E.W.

    1993-01-01

    The traditional undergraduate program for chemistry majors, especially at institutions devoted solely to undergraduate education, has limited space for 'special topics' courses in areas such as nuclear and radiochemistry. A scheme is proposed whereby the basic topics covered in an introductury radiochemistry course are touched upon, and in some cases covered in detail, at some time during the four-year sequence of courses taken by a chemistry major. (author) 6 refs.; 7 tabs

  4. The New Color of Chemistry: Green Chemistry

    OpenAIRE

    Zuhal GERÇEK

    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...

  5. Actinide/crown ether chemistry

    International Nuclear Information System (INIS)

    Benning, M.M.

    1988-01-01

    A structural survey of actinide/crown ether compounds was conducted in order to investigate the solid state chemistry of these complexes. Several parameters - the metal size, crown type, counterion, solvent systems and reaction and crystallization conditions - were varied to correlate their importance in complexation. Under atmospheric conditions, two types of complexes were isolated, those containing only hydrogen-bonded crown interactions and instances where the crown interacts directly with the metal center. In both cases, water seems to play a very important role. When coordinated to the metal, water molecules exhibit the necessary donor properties required for the formation of hydrogen-bonded contacts. The water molecules also provide fierce competition with the crown ethers for metal-binding sites and in most cases prohibit the formation of complexes in which direct metal-ligand association exists. The results of this study indicate that direct interaction between the metal atoms and the crown ethers, in the presence of water, can only occur with polyether conformations which limit the steric replusions within the metal coordination sphere

  6. 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...

  7. Integration of European Bond Markets

    DEFF Research Database (Denmark)

    Christiansen, Charlotte

    2014-01-01

    I investigate the time variation in the integration of EU government bond markets. The integration is measured by the explanatory power of European factor portfolios for the individual bond markets for each year. The integration of the government bond markets is stronger for EMU than non-EMU memb......I investigate the time variation in the integration of EU government bond markets. The integration is measured by the explanatory power of European factor portfolios for the individual bond markets for each year. The integration of the government bond markets is stronger for EMU than non...

  8. 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.

  9. Representational Classroom Practices that Contribute to Students' Conceptual and Representational Understanding of Chemical Bonding

    Science.gov (United States)

    Hilton, Annette; Nichols, Kim

    2011-11-01

    Understanding bonding is fundamental to success in chemistry. A number of alternative conceptions related to chemical bonding have been reported in the literature. Research suggests that many alternative conceptions held by chemistry students result from previous teaching; if teachers are explicit in the use of representations and explain their content-specific forms and functions, this might be avoided. The development of an understanding of and ability to use multiple representations is crucial to students' understanding of chemical bonding. This paper draws on data from a larger study involving two Year 11 chemistry classes (n = 27, n = 22). It explores the contribution of explicit instruction about multiple representations to students' understanding and representation of chemical bonding. The instructional strategies were documented using audio-recordings and the teacher-researcher's reflection journal. Pre-test-post-test comparisons showed an improvement in conceptual understanding and representational competence. Analysis of the students' texts provided further evidence of the students' ability to use multiple representations to explain macroscopic phenomena on the molecular level. The findings suggest that explicit instruction about representational form and function contributes to the enhancement of representational competence and conceptual understanding of bonding in chemistry. However, the scaffolding strategies employed by the teacher play an important role in the learning process. This research has implications for professional development enhancing teachers' approaches to these aspects of instruction around chemical bonding.

  10. Living GenoChemetics by hyphenating synthetic biology and synthetic chemistry in vivo.

    Science.gov (United States)

    Sharma, Sunil V; Tong, Xiaoxue; Pubill-Ulldemolins, Cristina; Cartmell, Christopher; Bogosyan, Emma J A; Rackham, Emma J; Marelli, Enrico; Hamed, Refaat B; Goss, Rebecca J M

    2017-08-09

    Marrying synthetic biology with synthetic chemistry provides a powerful approach toward natural product diversification, combining the best of both worlds: expediency and synthetic capability of biogenic pathways and chemical diversity enabled by organic synthesis. Biosynthetic pathway engineering can be employed to insert a chemically orthogonal tag into a complex natural scaffold affording the possibility of site-selective modification without employing protecting group strategies. Here we show that, by installing a sufficiently reactive handle (e.g., a C-Br bond) and developing compatible mild aqueous chemistries, synchronous biosynthesis of the tagged metabolite and its subsequent chemical modification in living culture can be achieved. This approach can potentially enable many new applications: for example, assay of directed evolution of enzymes catalyzing halo-metabolite biosynthesis in living cells or generating and following the fate of tagged metabolites and biomolecules in living systems. We report synthetic biological access to new-to-nature bromo-metabolites and the concomitant biorthogonal cross-coupling of halo-metabolites in living cultures.Coupling synthetic biology and chemical reactions in cells is a challenging task. The authors engineer bacteria capable of generating bromo-metabolites, develop a mild Suzuki-Miyaura cross-coupling reaction compatible with cell growth and carry out the cross-coupling chemistry in live cell cultures.

  11. 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.

  12. Amalgam shear bond strength to dentin using different bonding agents.

    Science.gov (United States)

    Vargas, M A; Denehy, G E; Ratananakin, T

    1994-01-01

    This study evaluated the shear bond strength of amalgam to dentin using five different bonding agents: Amalgambond Plus, Optibond, Imperva Dual, All-Bond 2, and Clearfil Liner Bond. Flat dentin surfaces obtained by grinding the occlusal portion of 50 human third molars were used for this study. To contain the amalgam on the tooth surface, cylindrical plastic molds were placed on the dentin and secured with sticky wax. The bonding agents were then applied according to the manufacturers' instructions or light activated and Tytin amalgam was condensed into the plastic molds. The samples were thermocycled and shear bond strengths were determined using an Instron Universal Testing Machine. Analysis by one-way ANOVA indicated significant difference between the five groups (P < 0.05). The bond strength of amalgam to dentin was significantly higher with Amalgambond Plus using the High-Performance Additive than with the other four bonding agents.

  13. 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.

  14. Application of Berlin's theorem to bond-length changes in isolated molecules and red- and blue-shifting H-bonded clusters

    Czech Academy of Sciences Publication Activity Database

    Wang, Weizhou; Hobza, Pavel

    2008-01-01

    Roč. 73, 6/7 (2008), s. 862-872 ISSN 0010-0765 R&D Projects: GA MŠk LC512; GA AV ČR IAA400550510 Institutional research plan: CEZ:AV0Z40550506 Keywords : Berlin's theorem * H-bonding * Blue -shifting H-bonding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.784, year: 2008

  15. Unwilling U-U bonding in U-2@C-80: cage-driven metal-metal bonds in di-uranium fullerenes

    Czech Academy of Sciences Publication Activity Database

    Foroutan-Nejad, C.; Vícha, J.; Marek, R.; Patzschke, M.; Straka, Michal

    2015-01-01

    Roč. 17, č. 37 (2015), s. 24182-24192 ISSN 1463-9076 R&D Projects: GA ČR(CZ) GA14-03564S Institutional support: RVO:61388963 Keywords : actinide-actinide bond * endohedral actinide fullerene * cage-driven bonding Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.449, year: 2015 http://pubs.rsc.org/en/content/articlepdf/2015/cp/c5cp04280a

  16. Antiparallel Dynamic Covalent Chemistries.

    Science.gov (United States)

    Matysiak, Bartosz M; Nowak, Piotr; Cvrtila, Ivica; Pappas, Charalampos G; Liu, Bin; Komáromy, Dávid; Otto, Sijbren

    2017-05-17

    The ability to design reaction networks with high, but addressable complexity is a necessary prerequisite to make advanced functional chemical systems. Dynamic combinatorial chemistry has proven to be a useful tool in achieving complexity, however with some limitations in controlling it. Herein we introduce the concept of antiparallel chemistries, in which the same functional group can be channeled into one of two reversible chemistries depending on a controllable parameter. Such systems allow both for achieving complexity, by combinatorial chemistry, and addressing it, by switching from one chemistry to another by controlling an external parameter. In our design the two antiparallel chemistries are thiol-disulfide exchange and thio-Michael addition, sharing the thiol as the common building block. By means of oxidation and reduction the system can be reversibly switched from predominantly thio-Michael chemistry to predominantly disulfide chemistry, as well as to any intermediate state. Both chemistries operate in water, at room temperature, and at mildly basic pH, which makes them a suitable platform for further development of systems chemistry.

  17. 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-...

  18. Stability of a metabolizable ester bond in radioimmunoconjugates

    International Nuclear Information System (INIS)

    Arano, Yasushi; Wakisaka, Kouji; Mukai, Takahiro; Uezono, Takashi; Motonari, Hiroshi; Akizawa, Hiromichi; Kairiyama, Claudia; Ohmomo, Yoshiro; Tanaka, Chiaki; Ishiyama, Munetaka; Sakahara, Harumi; Konishi, Junji; Yokoyama, Akira

    1996-01-01

    Ester bonds have been used as metabolizable linkages to reduce radioactivity levels in non-target tissues following the administration of antibodies labeled with metallic radionuclides. In this radiochemical design of antibodies, while the ester bonds should be cleaved rapidly in non-target tissues, high stability of the ester bonds in plasma is also required to preserve target radioactivity levels. To assess the structural requirements to stabilize the ester bond, a new benzyl-EDTA-derived bifunctional chelating agent with an ester bond, (1-[4-[4-(2-maleimidoethoxy)succinamido]benzyl]ethylenediamine-N,N,N',N'- tetraacetic acid; MESS-Bz-EDTA), was developed. MESS-Bz-EDTA was coupled with a thiolated monoclonal antibody (OST7, IgG 1 ) prepared by reducing its disulfide bonds to introduce the ester bond close and proximal to the antibody molecule. For comparison, 1-[4-(5-maleimidopentyl)aminobenzyl]ethylenediamine-N,N,N',N'-tetraacetic acid (EMCS-Bz-EDTA) and meleimidoethyl 3-[ 131 I]iodohippurate (MIH) was coupled to OST7 under the same conjunction chemistry. When incubated in 50% murine plasma or a buffered-solution of neutral pH, OST7-MESS-Bz-EDTA- 111 In rapidly released the radioactivity, and more than 95% of the initial radioactivity was liberated after a 24 h incubation in both solutions, due to a cleavage of the ester bond. On the other hand, only about 20% of the radioactivity was released from OST7-MIH- 131 I in both solutions during the same incubation period. In mice biodistribution studies, while a slightly faster radioactivity clearance from the blood with less radioactivity levels in the liver and kidneys was observed with OST7-MIH- 131 I than with OST7-EMCS-Bz-EDTA- 111 In, OST7-MESS-Bz-EDTA- 111 In indicated radioactivity clearance from the blood much faster than and almost comparable to that of OST7-MIH- 131 I and succinamidobenzyl-EDTA- 111 In, respectively. These findings as well as previous findings on radiolabeled antibodies with ester bonds

  19. Microshear bonding effectiveness of different dentin regions

    Directory of Open Access Journals (Sweden)

    Anelise F Montagner

    2015-01-01

    Full Text Available Aim: The aim of this in vitro study was to evaluate the influence of dentin surfaces with different tubule orientation on bond strength of a multimode adhesive system. Materials and Methods: Twenty human molars were selected and prepared in different ways in order to produce different dentin regions. The teeth were randomized (n = 5 according to the application modes of a multimode adhesive system (etch-and-rinse and self-etching and to the dentin region (occlusal and proximal - 1.5 mm depth from dentinoenamel junction. Cylindrical restorations were performed on dentin with a starch tube. The samples remained immersed in distilled water for 24 h and the microshear bond strength (μSBS test was performed. The μSBS values were expressed in MPa and analyzed with ANOVA and Tukey′s test (P < 0.05. Results: There was no significant difference in the bond strength values between the application modes of the adhesive system (P = 0.19; however, the dentin regions (P < 0.05 significantly affected the μSBS. The proximal dentin presented higher bond strength values than occlusal dentin. Conclusion: The dentin surfaces with different tubule orientation influenced the bonding effectiveness of the adhesive system tested.

  20. Bonding brackets to porcelain: in vitro study

    Directory of Open Access Journals (Sweden)

    Sant'Anna Eduardo Franzotti

    2002-01-01

    Full Text Available The aim of this research was to verify, in vitro, the effect of various porcelain surface treatments on the shear strength of orthodontic brackets bonded to porcelain and the mode of fracture after debonding. Eighty-eight samples of metallic supported feldspathic porcelain were randomly divided into four groups according to their surface preparation as follows: the porcelain was maintained intact (GI, roughened with a diamond bur (GII, etched with 10% hydrofluoric acid (GIII, or sandblasted with aluminum oxide (GIV. The specimens were treated with silane (Scothprime and brackets were bonded with Concise. Each sample was subjected to a shear load at a crosshead speed of 1 mm/min and a recording was made at the point of failure. Bond strengths, adequate to withstand the application of orthodontic forces, were achieved in all groups. The Kruskal-Wallis statistical test showed no significant differences in bond strength between the groups (p>0.05. However, many more porcelain fractures occurred on deglazed porcelain. This study indicates that with the appropriate material selection, the silane/composite procedure alone may be adequate for bonding.

  1. Fabrication and bonding of thiol-ene-based microfluidic devices

    International Nuclear Information System (INIS)

    Sikanen, Tiina M; Moilanen, Maria-Elisa; Lafleur, Josiane P; Zhuang, Guisheng; Jensen, Thomas G; Kutter, Jörg P

    2013-01-01

    In this work, the bonding strength of microchips fabricated by thiol-ene free-radical polymerization was characterized in detail by varying the monomeric thiol/allyl composition from the stoichiometric ratio (1:1) up to 100% excess of thiol (2:1) or allyl (1:2) functional groups. Four different thiol-ene to thiol-ene bonding combinations were tested by bonding: (i) two stoichiometric layers, (ii) two layers bearing complementary excess of thiols and allyls, (iii) two layers both bearing excess of thiols, or (iv) two layers both bearing excess of allyls. The results showed that the stiffness of the cross-linked polymer plays the most crucial role regarding the bonding strength. The most rigid polymer layers were obtained by using the stoichiometric composition or an excess of allyls, and thus, the bonding combinations (i) and (iv) withstood the highest pressures (up to the cut-off value of 6 bar). On the other hand, excess of thiol monomers yielded more elastic polymer layers and thus decreased the pressure tolerance for bonding combinations (ii) and (iii). By using monomers with more thiol groups (e.g. tetrathiol versus trithiol), a higher cross-linking ratio, and thus, greater stiffness was obtained. Surface characterization by infrared spectroscopy confirmed that the changes in the monomeric thiol/allyl composition were also reflected in the surface chemistry. The flexibility of being able to bond different types of thiol-enes together allows for tuning of the surface chemistry to yield the desired properties for each application. Here, a capillary electrophoresis separation is performed to demonstrate the attractive properties of stoichiometric thiol-ene microchips. (technical note)

  2. Development and Property Evaluation of Selected HfO2-Silicon and Rare Earth-Silicon Based Bond Coats and Environmental Barrier Coating Systems for SiC/SiC Ceramic Matrix Composites

    Science.gov (United States)

    Zhu, Dongming

    2016-01-01

    Ceramic environmental barrier coatings (EBC) and SiC/SiC ceramic matrix composites (CMCs) will play a crucial role in future aircraft propulsion systems because of their ability to significantly increase engine operating temperatures, improve component durability, reduce engine weight and cooling requirements. Advanced EBC systems for SiC/SiC CMC turbine and combustor hot section components are currently being developed to meet future turbine engine emission and performance goals. One of the significant material development challenges for the high temperature CMC components is to develop prime-reliant, high strength and high temperature capable environmental barrier coating bond coat systems, since the current silicon bond coat cannot meet the advanced EBC-CMC temperature and stability requirements. In this paper, advanced NASA HfO2-Si and rare earth Si based EBC bond coat EBC systems for SiC/SiC CMC combustor and turbine airfoil applications are investigated. High temperature properties of the advanced EBC systems, including the strength, fracture toughness, creep and oxidation resistance have been studied and summarized. The advanced NASA EBC systems showed some promise to achieve 1500C temperature capability, helping enable next generation turbine engines with significantly improved engine component temperature capability and durability.

  3. Uses of neutron scattering in supramolecular chemistry

    International Nuclear Information System (INIS)

    Lindoy, L.F.

    1998-01-01

    Full text: A major thrust in recent chemical research has been the development of supramolecular chemistry 1 - broadly the chemistry of large multicomponent molecular assemblies in which the component structural units are held together by either covalent linkages or by a variety of weaker (non-covalent) interactions that include hydrogen bonding, dipole stacking, π-stacking, van der Waals q forces and favourable hydrophobic interactions. Much of the activity in the area has been motivated by the known behaviour of biological molecules (such as enzymes). Thus molecular assemblies are ubiquitous in natural systems but, with a limited number of exceptions, have only recently been the subject of increasing investigation by chemists. A feature of much of this recent work has been its focus on molecular design for achieving complementarity between single molecule hosts and guests. The use of single crystal neutron diffraction coupled with molecular modelling and a range of other techniques to investigate the nature of individual supramolecular systems will be discussed. By way of example, in one such study the supramolecular array formed by co-crystallisation of 1,2- diaminoethane and benzoic acid has been investigated; the system self-assembles into an unusual layered structure composed of two-dimensional hydrogen bonded networks sandwiched between layers of edge-to-face stacked aromatic systems. The number of hydrogen-bond donors and acceptors is balanced in this structure

  4. Comparison of shear bond strength of the stainless steel metallic brackets bonded by three bonding systems

    Directory of Open Access Journals (Sweden)

    Mehdi Ravadgar

    2013-09-01

    Full Text Available Introduction: In orthodontic treatment, it is essential to establish a satisfactory bond between enamel and bracket. After the self-etch primers (SEPs were introduced for the facilitation of bracket bonding in comparison to the conventional etch-and-bond system, multiple studies have been carried out on their shear bond strengths which have yielded different results. This study was aimed at comparing shear bond strengths of the stainless steel metallic brackets bonded by three bonding systems. Methods: In this experimental in vitro study, 60 extracted human maxillary premolar teeth were randomly divided into three equal groups: in the first group, Transbond XT (TBXT light cured composite was bonded with Transbond plus self-etching primer (TPSEP in the second group, TBXT composite was bonded with the conventional method of acid etching and in the third group, the self cured composite Unite TM bonding adhesive was bonded with the conventional method of acid etching. In all the groups, Standard edgewise-022 metallic brackets (American Orthodontics, Sheboygan, USA were used. Twenty-four hours after the completion of thermocycling, shear bond strength of brackets was measured by Universal Testing Machine (Zwick. In order to compare the shear bond strengths of the groups, the variance analysis test (ANOVA was adopted and p≤0.05 was considered as a significant level. Results: Based on megapascal, the average shear bond strength for the first, second, and third groups was 8.27±1.9, 9.78±2, and 8.92±2.5, respectively. There was no significant difference in the shear bond strength of the groups. Conclusions: Since TPSEP shear bond strength is approximately at the level of the conventional method of acid etching and within the desirable range for orthodontic brackets shear bond strength, applying TPSEP can serve as a substitute for the conventional method of etch and bond, particularly in orthodontic operations.

  5. Comparison of shear bond strength of the stainless steel metallic brackets bonded by three bonding systems

    Directory of Open Access Journals (Sweden)

    Mehdi Ravadgar

    2013-09-01

    Full Text Available Introduction: In orthodontic treatment, it is essential to establish a satisfactory bond between enamel and bracket. After the self-etch primers (SEPs were introduced for the facilitation of bracket bonding in comparison to the conventional etch-and-bond system, multiple studies have been carried out on their shear bond strengths which have yielded different results. This study was aimed at comparing shear bond strengths of the stainless steel metallic brackets bonded by three bonding systems. Methods: In this experimental in vitro study, 60 extracted human maxillary premolar teeth were randomly divided into three equal groups: in the first group, Transbond XT (TBXT light cured composite was bonded with Transbond plus self-etching primer (TPSEP; in the second group, TBXT composite was bonded with the conventional method of acid etching; and in the third group, the self cured composite Unite TM bonding adhesive was bonded with the conventional method of acid etching. In all the groups, Standard edgewise-022 metallic brackets (American Orthodontics, Sheboygan, USA were used. Twenty-four hours after the completion of thermocycling, shear bond strength of brackets was measured by Universal Testing Machine (Zwick. In order to compare the shear bond strengths of the groups, the variance analysis test (ANOVA was adopted and p≤0.05 was considered as a significant level. Results: Based on megapascal, the average shear bond strength for the first, second, and third groups was 8.27±1.9, 9.78±2, and 8.92±2.5, respectively. There was no significant difference in the shear bond strength of the groups. Conclusions: Since TPSEP shear bond strength is approximately at the level of the conventional method of acid etching and within the desirable range for orthodontic brackets shear bond strength, applying TPSEP can serve as a substitute for the conventional method of etch and bond, particularly in orthodontic operations.

  6. Molecular recognition of nucleotides in micelles and the development and expansion of a chemistry outreach program

    Science.gov (United States)

    Schechinger, Linda Sue

    I. To investigate the delivery of nucleotide-based drugs, we are studying molecular recognition of nucleotide derivatives in environments that are similar to cell membranes. The Nowick group previously discovered that membrane-like surfactant micelles tetradecyltrimethylammonium bromide (TTAB) micelle facilitate molecular of adenosine monophosphate (AMP) recognition. The micelles bind nucleotides by means of electrostatic interactions and hydrogen bonding. We observed binding by following 1H NMR chemical shift changes of unique hexylthymine protons upon addition of AMP. Cationic micelles are required for binding. In surfactant-free or sodium dodecylsulfate solutions, no hydrogen bonding is observed. These observations suggest that the cationic surfactant headgroups bind the nucleotide phosphate group, while the intramicellar base binds the nucleotide base. The micellar system was optimized to enhance binding and selectivity for adenosine nucleotides. The selectivity for adenosine and the number of phosphate groups attached to the adenosine were both investigated. Addition of cytidine, guanidine, or uridine monophosphates, results in no significant downfield shifting of the NH resonance. Selectivity for the phosphate is limited, since adenosine mono-, di-, and triphosphates all have similar binding constants. We successfully achieved molecular recognition of adenosine nucleotides in micellar environments. There is significant difference in the binding interactions between the adenosine nucleotides and three other natural nucleotides. II. The UCI Chemistry Outreach Program (UCICOP) addresses the declining interest of the nations youth for science. UCICOP brings fun and exciting chemistry experiments to local high schools, to remind students that science is fun and has many practical uses. Volunteer students and alumni of UCI perform the demonstrations using scripts and material provided by UCICOP. The preparation of scripts and materials is done by two coordinators

  7. Radiation chemistry and its application

    International Nuclear Information System (INIS)

    Majima, Tetsuro

    2013-01-01

    Effects of radiation to human body have been seriously discussed nowadays. These are important issues for the realization of sustainable society. It should be emphasized that various reactive intermediates generated by radiation play important roles in each cases. Radiation chemical studies will provide various reaction-mechanistic aspects on these important issues. Our research group has continuously carried out reaction-mechanistic studies using radiation chemical methods. From these studies, we have obtained a variety of results on basic molecular systems, reactions, materials that are close to practical application, biological systems and so on. Reactive species are generated from the radiation reactions in solution, and can be used as one-electron oxidative and reductive reagent to give selectively radical cation and anion of solute molecules such as various organic and inorganic molecules. Therefore, the radiation chemistry has contributed significantly to chemistry in which one-electron oxidation and reduction play the important role. The kinetics of such redox processes and the following reduction play the important role. The kinetics of such redox processes and the following reactions can be studied in real time with the transition absorption measurement by the pulse radiolysis technique. Even though the target compounds cannot be oxidized and reduced in chemical or electrochemical oxidation and reduction, their one-electron redox can be performed by the electron beam radiation. Therefore, radiation chemistry is very useful technique for basic science. Moreover, application potentials of radiation chemistry are so high for various research subjects. Moreover, application potentials of radiation chemistry are so high for various research subjects

  8. Ion chemistry at elevated ion–molecule interaction energies in a selected ion flow-drift tube: reactions of H3O+, NO+ and O2+ with saturated aliphatic ketones

    Czech Academy of Sciences Publication Activity Database

    Spesyvyi, Anatolii; Smith, D.; Španěl, Patrik

    2017-01-01

    Roč. 19, č. 47 (2017), s. 31714-31723 ISSN 1463-9076 R&D Projects: GA ČR(CZ) GJ17-13157Y EU Projects: European Commission(XE) 674911 - IMPACT Institutional support: RVO:61388955 Keywords : reactions of H3O+, NO+ and O2+ * SIFT-MS Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 4.123, year: 2016

  9. S center dot center dot center dot N chalcogen bonded complexes of carbon disulfide with diazines. Theoretical study

    Czech Academy of Sciences Publication Activity Database

    Zierkiewicz, W.; Fanfrlík, Jindřich; Michalczyk, M.; Michalska, D.; Hobza, Pavel

    2018-01-01

    Roč. 500, Jan 26 (2018), s. 37-44 ISSN 0301-0104 Institutional support: RVO:61388963 Keywords : chalcogen bond * carbon disulfide * diazines * DFT Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 1.767, year: 2016

  10. Intermolecular Formation of Two C−C Bonds across Olefins Enabled by Boron-Based Relay Strategies

    Czech Academy of Sciences Publication Activity Database

    Hidasová, Denisa; Jahn, Ullrich

    2017-01-01

    Roč. 56, č. 33 (2017), s. 9656-9658 ISSN 1433-7851 Institutional support: RVO:61388963 Keywords : 1,2- metal ate rearrangement * C−C bond formation * radical reactions * transition metal catalysis * vinyl boronates Subject RIV: CC - Organic Chemistry OBOR OECD: Organic chemistry Impact factor: 11.994, year: 2016

  11. Twisted Amides: From Obscurity to Broadly Useful Transition-Metal-Catalyzed Reactions by N-C Amide Bond Activation.

    Science.gov (United States)

    Liu, Chengwei; Szostak, Michal

    2017-05-29

    The concept of using amide bond distortion to modulate amidic resonance has been known for more than 75 years. Two classic twisted amides (bridged lactams) ingeniously designed and synthesized by Kirby and Stoltz to feature fully perpendicular amide bonds, and as a consequence emanate amino-ketone-like reactivity, are now routinely recognized in all organic chemistry textbooks. However, only recently the use of amide bond twist (distortion) has advanced to the general organic chemistry mainstream enabling a host of highly attractive N-C amide bond cross-coupling reactions of broad synthetic relevance. In this Minireview, we discuss recent progress in this area and present a detailed overview of the prominent role of amide bond destabilization as a driving force in the development of transition-metal-catalyzed cross-coupling reactions by N-C bond activation. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Why are Hydrogen Bonds Directional?

    Indian Academy of Sciences (India)

    century and most chemists appear to think of 'chemi- cal bond' as ..... These complexes, in their global min- ima, have ... taneously act as hydrogen bond donor and acceptor displaying ... also has a local minimum, which is linear and similar to.

  13. Bond yield curve construction

    Directory of Open Access Journals (Sweden)

    Kožul Nataša

    2014-01-01

    Full Text Available In the broadest sense, yield curve indicates the market's view of the evolution of interest rates over time. However, given that cost of borrowing it closely linked to creditworthiness (ability to repay, different yield curves will apply to different currencies, market sectors, or even individual issuers. As government borrowing is indicative of interest rate levels available to other market players in a particular country, and considering that bond issuance still remains the dominant form of sovereign debt, this paper describes yield curve construction using bonds. The relationship between zero-coupon yield, par yield and yield to maturity is given and their usage in determining curve discount factors is described. Their usage in deriving forward rates and pricing related derivative instruments is also discussed.

  14. Longevity of Self-etch Dentin Bonding Adhesives Compared to Etch-and-rinse Dentin Bonding Adhesives: A Systematic Review.

    Science.gov (United States)

    Masarwa, Nader; Mohamed, Ahmed; Abou-Rabii, Iyad; Abu Zaghlan, Rawan; Steier, Liviu

    2016-06-01

    A systematic review and meta-analysis were performed to compare longevity of Self-Etch Dentin Bonding Adhesives to Etch-and-Rinse Dentin Bonding Adhesives. The following databases were searched for PubMed, MEDLINE, Web of Science, CINAHL, the Cochrane Library complemented by a manual search of the Journal of Adhesive Dentistry. The MESH keywords used were: "etch and rinse," "total etch," "self-etch," "dentin bonding agent," "bond durability," and "bond degradation." Included were in-vitro experimental studies performed on human dental tissues of sound tooth structure origin. The examined Self-Etch Bonds were of two subtypes; Two Steps and One Step Self-Etch Bonds, while Etch-and-Rinse Bonds were of two subtypes; Two Steps and Three Steps. The included studies measured micro tensile bond strength (μTBs) to evaluate bond strength and possible longevity of both types of dental adhesives at different times. The selected studies depended on water storage as the aging technique. Statistical analysis was performed for outcome measurements compared at 24 h, 3 months, 6 months and 12 months of water storage. After 24 hours (p-value = 0.051), 3 months (p-value = 0.756), 6 months (p-value=0.267), 12 months (p-value=0.785) of water storage self-etch adhesives showed lower μTBs when compared to the etch-and-rinse adhesives, but the comparisons were statistically insignificant. In this study, longevity of Dentin Bonds was related to the measured μTBs. Although Etch-and-Rinse bonds showed higher values at all times, the meta-analysis found no difference in longevity of the two types of bonds at the examined aging times. Copyright © 2016 Elsevier Inc. All rights reserved.

  15. Development of HIP bonding procedure and mechanical properties of HIP bonded joints for reduced activation ferritic steel F-82H

    International Nuclear Information System (INIS)

    Oda, Masahiro; Kurasawa, Toshimasa; Kuroda, Toshimasa; Hatano, Toshihisa; Takatsu, Hideyuki

    1997-03-01

    Structural materials of blanket components in fusion DEMO reactors will receive a neutron wall load more than 3-5MW/m 2 as well as exposed by surface heat flux more than 0.5MW/m 2 . 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.)

  16. Atomically Bonded Transparent Superhydrophobic Coatings

    Energy Technology Data Exchange (ETDEWEB)

    Aytug, Tolga [ORNL

    2015-08-01

    Maintaining clarity and avoiding the accumulation of water and dirt on optically transparent surfaces such as US military vehicle windshields, viewports, periscope optical head windows, and electronic equipment cover glasses are critical to providing a high level of visibility, improved survivability, and much-needed safety for warfighters in the field. Through a combination of physical vapor deposition techniques and the exploitation of metastable phase separation in low-alkali borosilicate, a novel technology was developed for the fabrication of optically transparent, porous nanostructured silica thin film coatings that are strongly bonded to glass platforms. The nanotextured films, initially structurally superhydrophilic, exhibit superior superhydrophobicity, hence antisoiling ability, following a simple but robust modification in surface chemistry. The surfaces yield water droplet contact angles as high as 172°. Moreover, the nanostructured nature of these coatings provides increased light scattering in the UV regime and reduced reflectivity (i.e., enhanced transmission) over a broad range of the visible spectrum. In addition to these functionalities, the coatings exhibit superior mechanical resistance to abrasion and are thermally stable to temperatures approaching 500°C. The overall process technology relies on industry standard equipment and inherently scalable manufacturing processes and demands only nontoxic, naturally abundant, and inexpensive base materials. Such coatings, applied to the optical components of current and future combat equipment and military vehicles will provide a significant strategic advantage for warfighters. The inherent self-cleaning properties of such superhydrophobic coatings will also mitigate biofouling of optical windows exposed to high-humidity conditions and can help decrease repair/replacement costs, reduce maintenance, and increase readiness by limiting equipment downtime.

  17. Atmospheric chemistry and climate

    OpenAIRE

    Satheesh, SK

    2012-01-01

    Atmospheric chemistry is a branch of atmospheric science where major focus is the composition of the Earth's atmosphere. Knowledge of atmospheric composition is essential due to its interaction with (solar and terrestrial) radiation and interactions of atmospheric species (gaseous and particulate matter) with living organisms. Since atmospheric chemistry covers a vast range of topics, in this article the focus is on the chemistry of atmospheric aerosols with special emphasis on the Indian reg...

  18. Polymer chemistry (revised edition)

    International Nuclear Information System (INIS)

    Kim, Jae Mum

    1987-02-01

    This book deals with polymer chemistry, which is divided into fourteen chapters. The contents of this book are development of polymer chemistry, conception of polymer, measurement of polymer chemistry, conception of polymer, measurement of polymer, molecule structure of polymer, thermal prosperities of solid polymer, basic theory of polymerization, radical polymerization, ion polymerization, radical polymerization, copolymerization, polymerization by step-reaction, polymer reaction, crown polymer and inorganic polymer on classification and process of creation such as polymeric sulfur and carbon fiber.

  19. Chemistry of the elements

    International Nuclear Information System (INIS)

    Greenwood, N.N.; Earnshaw, A.

    1984-01-01

    This textbook presents an account of the chemistry of the elements for both undergraduate and postgraduate students. It covers not only the 'inorganic' chemistry of the elements, but also analytical, theoretical, industrial, organometallic;, bio-inorganic and other areas of chemistry which apply. The following elements of special nuclear interest are included: Rb, Cs, Fr, Sr, Ba, Ra, Po, At, Rn, Sc, Y, Zr, Hf, V, Nb, Ta, Mo, Tc, Ru, the Lanthanide Elements, the Actinide Elements. (U.K.)

  20. Corporate Hybrid Bonds

    OpenAIRE

    Ahlberg, Johan; Jansson, Anton

    2016-01-01

    Hybrid securities do not constitute a new phenomenon in the Swedish capital markets. Most commonly, hybrids issued by Swedish real estate companies in recent years are preference shares. Corporate hybrid bonds on the other hand may be considered as somewhat of a new-born child in the family of hybrid instruments. These do, as all other hybrid securities, share some equity-like and some debt-like characteristics. Nevertheless, since 2013 the interest for the instrument has grown rapidly and ha...