WorldWideScience

Sample records for atom transfer chemistry

  1. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1993-01-01

    Advances in Electron Transfer Chemistry, Volume 3 presents studies that discuss findings in the various aspects of electron chemistry. The book is comprised of four chapters; each chapter reviews a work that tackles an issue in electron transfer chemistry. Chapter 1 discusses the photoinduced electron transfer in flexible biaryl donor-acceptor molecules. Chapter 2 tackles light-induced electron transfer in inorganic systems in homogeneous and heterogeneous phases. The book also covers internal geometry relaxation effects on electron transfer rates of amino-centered systems. The sequential elec

  2. Oxygen-atom transfer chemistry and thermolytic properties of a di-tert-butylphosphate-ligated Mn4O4 cubane.

    Science.gov (United States)

    Van Allsburg, Kurt M; Anzenberg, Eitan; Drisdell, Walter S; Yano, Junko; Tilley, T Don

    2015-03-16

    [Mn4O4{O2P(OtBu)2}6] (1), an Mn4O4 cubane complex combining the structural inspiration of the photosystem II oxygen-evolving complex with thermolytic precursor ligands, was synthesized and fully characterized. Core oxygen atoms within complex 1 are transferred upon reaction with an oxygen-atom acceptor (PEt3), to give the butterfly complex [Mn4O2{O2P(OtBu)2}6(OPEt3)2]. The cubane structure is restored by reaction of the latter complex with the O-atom donor PhIO. Complex 1 was investigated as a precursor to inorganic Mn metaphosphate/pyrophosphate materials, which were studied by X-ray absorption spectroscopy to determine the fate of the Mn4O4 unit. Under the conditions employed, thermolyses of 1 result in reduction of the manganese to Mn(II) species. Finally, the related butterfly complex [Mn4O2{O2P(pin)}6(bpy)2] (pin = pinacolate) is described.

  3. The Unique Gas-Phase Chemistry of the [AuO](+) /CH4 Couple: Selective Oxygen-Atom Transfer to, Rather than Hydrogen-Atom Abstraction from, Methane.

    Science.gov (United States)

    Zhou, Shaodong; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2016-08-26

    The thermal reaction of [AuO](+) with methane has been explored using FT-ICR mass spectrometry complemented by high-level quantum chemical calculations. In contrast to the previously studied congener [CuO](+) , and to [AgO](+) , [AuO](+) reacts with CH4 exclusively via oxygen-atom transfer to form CH3 OH, and a novel mechanistic scenario for this selective oxidation process has been revealed. Also, the origin of the inertness of the [AgO](+) /CH4 couple has been addressed computationally.

  4. Facile synthesis of dendrimer-like star-branched poly(isopropylacrylamide) via combination of click chemistry and atom transfer radical polymerization

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    We report a facile synthesis method of dendrimer-like star-branched poly(N-isopropylacrylamide) (PNIPAM) via the combination of click chemistry and atom transfer radical polymerization (ATRP) by employing the arm-first approach.First,the α-azido-ω-chloro-heterodifunctionalized building block,N3-PNIPAM-Cl (G0-Cl),was synthesized via ATRP by 3-azidopropyl 2-chloropropionate as the initiator.Taking advantage of click chemistry,the first generation (G1) of dendrimer-like star-branched PNIPAM,G1-(Cl)3,was facilely prepared via the click coupling reaction between G0-Cl and tripropargylamine.For the construction of second generation (G2) dendrimer-like star-branched PNIPAM,G2-(Cl)6,terminal chloride moieties of G1-(Cl)3 were first converted to azide,and then reacted with excess tripropargylamine to give G1-(alkynyl)6 ;G2-(Cl)6 was subsequently prepared via click reaction between G1-(alkynyl) 6 and G0-Cl.Gel permeation chromatography (GPC) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry were employed to confirm the successful construction of dendrimer-like star-branched polymers.The unique thermal phase transition behavior of this dendrimer-like star-branched polymer in aqueous solutions was further investigated by turbidimetry and micro-differential scanning calorimetry (Micro-DSC).

  5. Computational chemistry and aeroassisted orbital transfer vehicles

    Science.gov (United States)

    Cooper, D. M.; Jaffe, R. L.; Arnold, J. O.

    1985-01-01

    An analysis of the radiative heating phenomena encountered during a typical aeroassisted orbital transfer vehicle (AOTV) trajectory was made to determine the potential impact of computational chemistry on AOTV design technology. Both equilibrium and nonequilibrium radiation mechanisms were considered. This analysis showed that computational chemistry can be used to predict (1) radiative intensity factors and spectroscopic data; (2) the excitation rates of both atoms and molecules; (3) high-temperature reaction rate constants for metathesis and charge exchange reactions; (4) particle ionization and neutralization rates and cross sections; and (5) spectral line widths.

  6. Advances in electron transfer chemistry

    CERN Document Server

    Mariano, Patrick S

    1995-01-01

    Advances in Electron Transfer Chemistry, Volume 4 presents the reaction mechanisms involving the movement of single electrons. This book discusses the electron transfer reactions in organic, biochemical, organometallic, and excited state systems. Organized into four chapters, this volume begins with an overview of the photochemical behavior of two classes of sulfonium salt derivatives. This text then examines the parameters that control the efficiencies for radical ion pair formation. Other chapters consider the progress in the development of parameters that control the dynamics and reaction p

  7. Visualizing materials chemistry at atomic resolution.

    Science.gov (United States)

    Sanchez, Sergio I; Small, Matthew W; Sivaramakrishnan, Shankar; Wen, Jian-guo; Zuo, Jian-Min; Nuzzo, Ralph G

    2010-04-01

    Analytical electron microscopy--empowered by advances in electron optics and detectors--is poised to radically transform our understanding of the complex phenomena arising from atomic and electronic structure in materials chemistry. (To listen to a podcast about this article, please go to the Analytical Chemistry multimedia page at pubs.acs.org/page/ancham/audio/index.html.).

  8. Efficient transfer of francium atoms

    Science.gov (United States)

    Aubin, Seth; Behr, John; Gorelov, Alexander; Pearson, Matt; Tandecki, Michael; Collister, Robert; Gwinner, Gerald; Shiells, Kyle; Gomez, Eduardo; Orozco, Luis; Zhang, Jiehang; Zhao, Yanting; FrPNC Collaboration

    2016-05-01

    We report on the progress of the FrPNC collaboration towards Parity Non Conservation Measurements (PNC) using francium atoms at the TRIUMF accelerator. We demonstrate efficient transfer (higher than 40%) to the science vacuum chamber where the PNC measurements will be performed. The transfer uses a downward resonant push beam from the high-efficiency capture magneto optical trap (MOT) towards the science chamber where the atoms are recaptured in a second MOT. The transfer is very robust with respect to variations in the parameters (laser power, detuning, alignment, etc.). We accumulate a growing number of atoms at each transfer pulse (limited by the lifetime of the MOT) since the push beam does not eliminate the atoms already trapped in the science MOT. The number of atoms in the science MOT is on track to meet the requirements for competitive PNC measurements when high francium rates (previously demonstrated) are delivered to our apparatus. The catcher/neutralizer for the ion beam has been tested reliably to 100,000 heating/motion cycles. We present initial tests on the direct microwave excitation of the ground hyperfine transition at 45 GHz. Support from NSERC and NRC from Canada, NSF and Fulbright from USA, and CONACYT from Mexico.

  9. Oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives by nitrous oxide via selective oxygen atom transfer reactions: insights from quantum chemistry calculations.

    Science.gov (United States)

    Xie, Hujun; Liu, Chengcheng; Yuan, Ying; Zhou, Tao; Fan, Ting; Lei, Qunfang; Fang, Wenjun

    2016-01-21

    The mechanisms for the oxidation of phenyl and hydride ligands of bis(pentamethylcyclopentadienyl)hafnium derivatives (Cp* = η(5)-C5Me5) by nitrous oxide via selective oxygen atom transfer reactions have been systematically studied by means of density functional theory (DFT) calculations. On the basis of the calculations, we investigated the original mechanism proposed by Hillhouse and co-workers for the activation of N2O. The calculations showed that the complex with an initial O-coordination of N2O to the coordinatively unsaturated Hf center is not a local minimum. Then we proposed a new reaction mechanism to investigate how N2O is activated and why N2O selectively oxidize phenyl and hydride ligands of . Frontier molecular orbital theory analysis indicates that N2O is activated by nucleophilic attack by the phenyl or hydride ligand. Present calculations provide new insights into the activation of N2O involving the direct oxygen atom transfer from nitrous oxide to metal-ligand bonds instead of the generally observed oxygen abstraction reaction to generate metal-oxo species.

  10. Highly regioselective hydride transfer, oxidative dehydrogenation, and hydrogen-atom abstraction in the thermal gas-phase chemistry of [Zn(OH)](+)/C3H8.

    Science.gov (United States)

    Wu, Xiao-Nan; Zhao, Hai-Tao; Li, Jilai; Schlangen, Maria; Schwarz, Helmut

    2014-12-28

    The thermal reactions of [Zn(OH)](+) with C3H8 have been studied by means of gas-phase experiments and computational investigation. Two types of C-H bond activation are observed in the experiment, and pertinent mechanistic features include inter alia: (i) the metal center of [Zn(OH)](+) serves as active site in the hydride transfer to generate [i-C3H7](+) as major product, (ii) generally, a high regioselectivity is accompanied by remarkable chemoselectivity: for example, the activation of a methyl C-H bond results mainly in the formation of water and [Zn(C3,H7)](+). According to computational work, this ionic product corresponds to [HZn(CH3CH=CH2)](+). Attack of the zinc center at a secondary C-H bond leads preferentially to hydride transfer, thus giving rise to the generation of [i-C3H7](+); (iii) upon oxidative dehydrogenation (ODH), liberation of CH3CH2=CH2 occurs to produce [HZn(H2O)](+). Both, ODH as well as H2O loss proceed through the same intermediate which is characterized by the fact that a methylene hydrogen atom from the substrate is transferred to the zinc and one hydrogen atom from the methyl group to the OH group of [Zn(OH)](+). The combined experimental/computational gas-phase study of C-H bond activation by zinc hydroxide provides mechanistic insight into related zinc-catalyzed large-scale processes and identifies the crucial role that the Lewis-acid character of zinc plays.

  11. Carborane complexes of ruthenium(III): studies on thermal reaction chemistry and the catalyst design for atom transfer radical polymerization of methyl methacrylate.

    Science.gov (United States)

    Grishin, Ivan D; D'yachihin, Dmitrii I; Piskunov, Alexander V; Dolgushin, Fedor M; Smol'yakov, Alexander F; Il'in, Mikhail M; Davankov, Vadim A; Chizhevsky, Igor T; Grishin, Dmitry F

    2011-08-15

    The heating of the 18-electron complex [3,3-(dppb)-3-H-3-Cl-closo-3,1,2-RuC(2)B(9)H(11)] (3) in benzene at 80 °C in the presence of a small amount of CCl(4) as initiator afforded paramagnetic 17-electron species [3,3-(dppb)-3-Cl-closo-3,1,2-RuC(2)B(9)H(11)] (4) along with minor amounts of two P-phenylene ortho-cycloboronated derivatives [3-Cl-3,3,8-{Ph(2)P(CH(2))(4)PPh-μ-(C(6)H(4)-ortho)}-closo-3,1,2-RuC(2)B(9)H(10)] (5) and [3,7-Cl(2)-3,3,8-{Ph(2)P(CH(2))(4)PPh-μ-(C(6)H(4)-ortho)}-closo-3,1,2-RuC(2)B(9)H(10)] (6) in total yield of ca. 80%. The heating of either 3 or 4 in toluene at 95 °C in the absence of CCl(4) led to the selective formation of 5, which was isolated in 64% and 46% yield, respectively. Thermolysis of 3 at higher temperatures (boiling toluene, 110 °C) gives novel paramagnetic species [3-Cl-3,3,7,8-{Ph(2)P(CH(2))(4)P-μ-(C(6)H(4)-ortho)(2)}-closo-3,1,2-RuC(2)B(9)H(9)] (7) featuring bis(ortho-cycloboronation) of both P-phenyl groups at the same phosphorus atom of the ruthenium-bound dppb ligand. All new paramagnetic complexes 4-7, as well as starting diamagnetic species 3, were characterized by single-crystal X-ray diffraction and, in addition, by EPR spectroscopic studies of odd-electron complexes. Ruthenacarboranes 3-5 and 7 all display high efficiency as catalysts for the atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA). Complex 5 gave the best catalyst performance in terms of polydispersity; the PDI (M(w)/M(n)) of the polymer samples is as low as 1.15.

  12. Advances in electron transfer chemistry, v.6

    CERN Document Server

    Mariano, PS

    1999-01-01

    It is clear that electron transfer chemisty is now one of the most active areas of chemical study. Advances in Electron Transfer Chemistry has been designed to allow scientists who are developing new knowledge in this rapidly expanding area to describe their most recent research findings. This volume will serve those interested in learning about current breakthroughs in this rapidly expanding area of chemical research.

  13. Atom transfer as a preparative tool in coordination chemistry. Synthesis and characterization of Cr(V) nitrido complexes of bidentate ligands

    DEFF Research Database (Denmark)

    Birk, Torben; Bendix, Jesper

    2003-01-01

    The transfer of a terminal nitrido ligand from MnV(N)(salen) to Cr(III) complexes is explored as a new preparative route to CrV nitrido complexes. Reaction of MnV(N)(salen) with labile CrCl3(THF)3 in acetonitrile solution precipitate [Mn(Cl)(salen)]·(CH3CN) and yields a solution containing a mixt...

  14. Surface functionalized SiO2 nanoparticles with cationic polymers via the combination of mussel inspired chemistry and surface initiated atom transfer radical polymerization: Characterization and enhanced removal of organic dye.

    Science.gov (United States)

    Huang, Qiang; Liu, Meiying; Mao, Liucheng; Xu, Dazhuang; Zeng, Guangjian; Huang, Hongye; Jiang, Ruming; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-03-28

    Monodispersed SiO2 particles functionalized with cationic polymers poly-((3-acrylamidopropyl)trimethylammonium chloride) (PAPTCl) were prepared using mussel inspired surface modification strategy and surface initiated atom transfer radical polymerization (SI-ATRP). Fourier transform infrared spectroscopy, transmission electron microscope, thermogravimetric analysis, X-ray photoelectron spectroscopy, and zeta potential were employed to characterize these SiO2 samples. The adsorption performance of the functionalized SiO2 (donated as SiO2-PDA-PAPTCl) towards anionic organic dye Congo red (CR) was investigated to evaluate their potential environmental applications. We demonstrated that the surface of SiO2 particles can be successfully functionalized with cationic PAPTCl. The adsorption capability of as-prepared SiO2 was found to increases from 28.70 and 106.65mg/g after surface grafted with cationic polymers. The significant enhancement in the adsorption capability of SiO2-PDA-PAPTCl is mainly attributed to the introduction of cationic polymers. More importantly, this strategy is expected to be promising for fabrication of many other functional polymer nanocomposites for environmental applications due to the universality of mussel inspired chemistry and well designability and good monomer adaptability of SI-ATRP.

  15. Transfer in chemistry: a study of students' abilities in transferring mathematical knowledge to chemistry

    Science.gov (United States)

    Hoban, Richard A.; Finlayson, Odilla E.; Nolan, Brien C.

    2013-01-01

    It is recognized that there is a mathematics problem in chemistry, whereby, for example, undergraduate students appear to be unable to utilize basic calculus knowledge in a chemistry context - calculus knowledge - which would have been taught to these students in a mathematics context. However, there appears to be a scarcity of literature addressing the possible reasons for this problem. This dearth of literature has spurred the following two questions: (1) Can students transfer mathematical knowledge to chemistry?; and (2) What are the possible factors associated with students being able to successfully transfer mathematical knowledge to a chemistry context? These questions were investigated in relation to the basic mathematical knowledge which chemistry students need for chemical kinetics and thermodynamics, using the traditional view of the transfer of learning. Two studies were undertaken amongst two samples of undergraduate students attending Dublin City University. Findings suggest that the mathematical difficulties which students encounter in a chemistry context may not be because of an inability to transfer the knowledge, but may instead be due to insufficient mathematical understanding and/or knowledge of mathematical concepts relevant to chemical kinetics and thermodynamics.

  16. Presentation of Atomic Structure in Turkish General Chemistry Textbooks

    Science.gov (United States)

    Niaz, Mansoor; Costu, Bayram

    2009-01-01

    Research in science education has recognized the importance of teaching atomic structure within a history and philosophy of science perspective. The objective of this study is to evaluate general chemistry textbooks published in Turkey based on the eight criteria developed in previous research. Criteria used referred to the atomic models of…

  17. Hydropersulfides: H-Atom Transfer Agents Par Excellence.

    Science.gov (United States)

    Chauvin, Jean-Philippe R; Griesser, Markus; Pratt, Derek A

    2017-05-10

    Hydropersulfides (RSSH) are formed endogenously via the reaction of the gaseous biotransmitter hydrogen sulfide (H2S) and disulfides (RSSR) and/or sulfenic acids (RSOH). RSSH have been investigated for their ability to store H2S in vivo and as a line of defense against oxidative stress, from which it is clear that RSSH are much more reactive to two-electron oxidants than thiols. Herein we describe the results of our investigations into the H-atom transfer chemistry of RSSH, contrasting it with the well-known H-atom transfer chemistry of thiols. In fact, RSSH are excellent H-atom donors to alkyl (k ∼ 5 × 10(8) M(-1) s(-1)), alkoxyl (k ∼ 1 × 10(9) M(-1) s(-1)), peroxyl (k ∼ 2 × 10(6) M(-1) s(-1)), and thiyl (k > 1 × 10(10) M(-1) s(-1)) radicals, besting thiols by as little as 1 order and as much as 4 orders of magnitude. The inherently high reactivity of RSSH to H-atom transfer is based largely on thermodynamic factors; the weak RSS-H bond dissociation enthalpy (∼70 kcal/mol) and the associated high stability of the perthiyl radical make the foregoing reactions exothermic by 15-34 kcal/mol. Of particular relevance in the context of oxidative stress is the reactivity of RSSH to peroxyl radicals, where favorable thermodynamics are bolstered by a secondary orbital interaction in the transition state of the formal H-atom transfer that drives the inherent reactivity of RSSH to match that of α-tocopherol (α-TOH), nature's premier radical-trapping antioxidant. Significantly, the reactivity of RSSH eclipses that of α-TOH in H-bond-accepting media because of their low H-bond acidity (α2(H) ∼ 0.1). This affords RSSH a unique versatility compared to other highly reactive radical-trapping antioxidants (e.g., phenols, diarylamines, hydroxylamines, sulfenic acids), which tend to have high H-bond acidities. Moreover, the perthiyl radicals that result are highly persistent under autoxidation conditions and undergo very rapid dimerization (k = 5 × 10(9) M(-1) s(-1

  18. Dynamics of the Chemistry of Electronically Excited Atoms in Defined Quantum States.

    Science.gov (United States)

    1978-05-01

    laser development . In essence, this research concerns itself with the elucidation of the role of electronic energy in affecting the chemistry or photochemistry of excited halogen atoms and molecules. While much is known about the dynamics of chemical and physical processes which are carried out on the lowest potential energy hypersurface correlating with reactants and products in their electronic ground state, relatively little is known about the dynamics of such phenomena as energy transfer and chemical reactivity on higher-lying potential

  19. Beyond organic chemistry: aromaticity in atomic clusters.

    Science.gov (United States)

    Boldyrev, Alexander I; Wang, Lai-Sheng

    2016-04-28

    We describe joint experimental and theoretical studies carried out collaboratively in the authors' labs for understanding the structures and chemical bonding of novel atomic clusters, which exhibit aromaticity. The concept of aromaticity was first discovered to be useful in understanding the square-planar unit of Al4 in a series of MAl4(-) bimetallic clusters that led to discoveries of aromaticity in many metal cluster systems, including transition metals and similar cluster motifs in solid compounds. The concept of aromaticity has been found to be particularly powerful in understanding the stability and bonding in planar boron clusters, many of which have been shown to be analogous to polycyclic aromatic hydrocarbons in their π bonding. Stimulated by the multiple aromaticity in planar boron clusters, a design principle has been proposed for stable metal-cerntered aromatic molecular wheels of the general formula, M@Bn(k-). A series of such borometallic aromatic wheel complexes have been produced in supersonic cluster beams and characterized experimentally and theoretically, including Ta@B10(-) and Nb@B10(-), which exhibit the highest coordination number in two dimensions.

  20. Soliton Atom Laser with Quantum State Transfer Property

    Institute of Scientific and Technical Information of China (English)

    LIU Xiong-Jun; JING Hui; GE Mo-Lin

    2006-01-01

    @@ We study the nonlinear effects in the quantum states transfer technique from photons to matter waves in the three-level case, which may provide the formation of a soliton atom laser with nonclassical atoms. The validity of quantum transfer mechanism is confirmed in the presence of the intrinsic nonlinear atomic interactions. The accompanied frequency chirp effect is shown to have no influence on the grey solitons formed by the output atom laser and the possible quantum depletion effect is also briefly discussed.

  1. Transfer printing of DNA by "click" chemistry

    NARCIS (Netherlands)

    Rozkiewicz, D.I.; Gierlich, Johannes; Burley, Glenn A.; Gutschmiedl, Katrin; Carell, Thomas; Ravoo, B.J.; Reinhoudt, David

    2007-01-01

    This paper describes a straightforward procedure to immobilize oligonucleotides on glass substrates in well-defined micropatterns by microcontact printing with a dendrimer-modified stamp. The oligonucleotides are efficiently immobilized by click chemistry induced by microcontact printing.

  2. An environmental transfer hub for multimodal atom probe tomography.

    Science.gov (United States)

    Perea, Daniel E; Gerstl, Stephan S A; Chin, Jackson; Hirschi, Blake; Evans, James E

    2017-01-01

    Environmental control during transfer between instruments is required for samples sensitive to air or thermal exposure to prevent morphological or chemical changes prior to analysis. Atom probe tomography is a rapidly expanding technique for three-dimensional structural and chemical analysis, but commercial instruments remain limited to loading specimens under ambient conditions. In this study, we describe a multifunctional environmental transfer hub allowing controlled cryogenic or room-temperature transfer of specimens under atmospheric or vacuum pressure conditions between an atom probe and other instruments or reaction chambers. The utility of the environmental transfer hub is demonstrated through the acquisition of previously unavailable mass spectral analysis of an intact organic molecule made possible via controlled cryogenic transfer into the atom probe using the hub. The ability to prepare and transfer specimens in precise environments promises a means to access new science across many disciplines from untainted samples and allow downstream time-resolved in situ atom probe studies.

  3. An environmental transfer hub for multimodal atom probe tomography

    Energy Technology Data Exchange (ETDEWEB)

    Perea, Daniel E.; Gerstl, Stephan S. A.; Chin, Jackson; Hirschi, Blake; Evans, James. E.

    2017-05-02

    Environmental control during transfer between instruments is required for specimens sensitive to air or thermal exposure to prevent morphological or chemical changes. Atom Probe Tomography is an expanding technique but commercial instruments remain limited to loading under ambient conditions. Here we describe a multifunctional environmental transfer hub allowing controlled cryogenic, atmospheric and vacuum transfer between an Atom Probe and other instruments containing separate chambers to allow downstream time-resolved in-situ studies.

  4. Getting the chemistry right: protonation, tautomers and the importance of H atoms in biological chemistry.

    Science.gov (United States)

    Bax, Ben; Chung, Chun Wa; Edge, Colin

    2017-02-01

    There are more H atoms than any other type of atom in an X-ray crystal structure of a protein-ligand complex, but as H atoms only have one electron they diffract X-rays weakly and are `hard to see'. The positions of many H atoms can be inferred by our chemical knowledge, and such H atoms can be added with confidence in `riding positions'. For some chemical groups, however, there is more ambiguity over the possible hydrogen placements, for example hydroxyls and groups that can exist in multiple protonation states or tautomeric forms. This ambiguity is far from rare, since about 25% of drugs have more than one tautomeric form. This paper focuses on the most common, `prototropic', tautomers, which are isomers that readily interconvert by the exchange of an H atom accompanied by the switch of a single and an adjacent double bond. Hydrogen-exchange rates and different protonation states of compounds (e.g. buffers) are also briefly discussed. The difference in heavy (non-H) atom positions between two tautomers can be small, and careful refinement of all possible tautomers may single out the likely bound ligand tautomer. Experimental methods to determine H-atom positions, such as neutron crystallography, are often technically challenging. Therefore, chemical knowledge and computational approaches are frequently used in conjugation with experimental data to deduce the bound tautomer state. Proton movement is a key feature of many enzymatic reactions, so understanding the orchestration of hydrogen/proton motion is of critical importance to biological chemistry. For example, structural studies have suggested that, just as a chemist may use heat, some enzymes use directional movement to protonate specific O atoms on phosphates to catalyse phosphotransferase reactions. To inhibit `wriggly' enzymes that use movement to effect catalysis, it may be advantageous to have inhibitors that can maintain favourable contacts by adopting different tautomers as the enzyme `wriggles'.

  5. Infusing the Chemistry Curriculum with Green Chemistry Using Real-World Examples, Web Modules, and Atom Economy in Organic Chemistry Courses

    Science.gov (United States)

    Cann, Michael C.; Dickneider, Trudy A.

    2004-01-01

    Green chemistry is the awareness of the damaging environmental effects due to chemical research and inventions. There is emphasis on a need to include green chemistry in synthesis with atom economy in organic chemistry curriculum to ensure an environmentally conscious future generation of chemists, policy makers, health professionals and business…

  6. Robust population transfer in atomic beams induced by Doppler shifts

    Science.gov (United States)

    Unanyan, R. G.

    2016-10-01

    The influence of photon momentum recoil on adiabatic population transfer in an atomic three-level lambda system is studied. It is shown that the Doppler frequency shifts, due to atomic motion, can play an important role in adiabatic population transfer processes of atomic internal states by a pair of laser fields. For the limiting case of slow atoms (Doppler shift much smaller than the photon recoil energy), the atoms occupy the same target state regardless of the order of switching of laser fields, while for the case of fast atoms interacting with the intuitive sequence of pulses, the target state is the intermediate atomic state. Furthermore, it is shown that this novel technique for adiabatic population transfer is related to a level crossing in the bright-intermediate state basis (rather than in the original atomic basis). It is shown that these processes are robust with respect to parameter fluctuations, such as the laser pulse area and the relative spatial offset (delay) of the laser beams. The obtained results can be used for the control of temporal evolution of atomic populations in cold atomic beams by externally adjustable Doppler shifts.

  7. Pickering emulsion templated interfacial atom transfer radical polymerization for microencapsulation.

    Science.gov (United States)

    Li, Jian; Hitchcock, Adam P; Stöver, Harald D H

    2010-12-01

    This Article describes a new microencapsulation method based on a Pickering emulsion templated interfacial atom transfer radical polymerization (PETI-ATRP). Cationic LUDOX CL nanoparticles were coated electrostatically with an anionic polymeric ATRP initiator, poly(sodium styrene sulfonate-co-2-(2-bromoisobutyryloxy)ethyl methacrylate) (PSB), prepared by radical copolymerization of sodium styrene sulfonate and 2-(2-bromoisobutyryloxy)ethyl methacrylate (BIEM). The resulting PSB-modified CL particles were surface active and could be used to stabilize oil-in-water Pickering emulsions. ATRP of water-soluble cross-linking monomers, confined to the oil-water interface by the surface-bound PSB, then led to nanoparticle/polymer composite shells. This method allowed encapsulation of core solvents (xylene, hexadecane, perfluoroheptane) with different solubility parameters. The microcapsule (MC) wall chemistry could accommodate different monomers, demonstrating the versatility of this method. Double-walled MCs were formed by sequentially carrying out PETI-ATRP and in situ polymerization of encapsulated monomers. The double-walled structure was verified by both transmission electron microscopy (TEM) and scanning transmission X-ray microscopy (STXM).

  8. Let Students Derive, by Themselves, Two-Dimensional Atomic and Molecular Quantum Chemistry from Scratch

    Science.gov (United States)

    Ge, Yingbin

    2016-01-01

    Hands-on exercises are designed for undergraduate physical chemistry students to derive two-dimensional quantum chemistry from scratch for the H atom and H[subscript 2] molecule, both in the ground state and excited states. By reducing the mathematical complexity of the traditional quantum chemistry teaching, these exercises can be completed…

  9. Electron transfer in ion-atom collisions

    Energy Technology Data Exchange (ETDEWEB)

    Lin, C D

    1979-01-01

    Recent theoretical development in the understanding of electron transfer processes is reviewed. K-K electron transfer processes are studied for projectiles (nuclear charge Z/sub B/) and targets (nuclear charge Z/sub A/) in which Z/sub A/ and Z/sub B/ range from Z/sub A/ much greater than Z/sub B/ to Z/sub A/ approx. = Z/sub B/, over the energy range 0.1 < v/v/sub e/ < 2. (GHT)

  10. Marcus wins nobel prize in chemistry for electron transfer theory

    Energy Technology Data Exchange (ETDEWEB)

    Levi, B.G.

    1993-01-01

    This article describes the work of Rudolf Marcus of Caltech leading to his receipt of the 1992 Nobel Prize in Chemistry [open quotes]for his contributions to the theory of electron transfer reactions in chemical systems.[close quotes] Applications of Marcus' theory include such diverse phenomena as photosynthesis, electrically conducting polymers, chemiluminescence, and corrosion. Historical aspects of his career are given. 10 refs., 1 fig.

  11. H atom transfer of collinear OH…O system

    Institute of Scientific and Technical Information of China (English)

    WU, Tao(吴韬); CHEN, Xian-Yang(陈先阳); PENG, Jian-Bo(彭建波); JU, Guan-Zhi(居冠之); JU, Guan-Zhi(居冠之)

    2000-01-01

    A quantum mechanical calculation was performed to study the hydrogen atom transfer of collinear OH…O/OD…O system,for which Delves ' coordinates and R-matrix propagation method were applied in a Melius-Blint potential energy surface. The calculation result showed that the state-state H atom transfer probability comported strong oscillation phenomena and collision delay time of the title system was in the fs-ps time scale. The kinetic isotope effect was calculated in this work too.

  12. Living atom transfer radical polymerization of 4-acetoxystyrene

    DEFF Research Database (Denmark)

    Gao, Bo; Chen, Xianyi; Ivan, Bela

    1997-01-01

    Living atom transfer radical polymerization (ATRP) of 4-acetoxystyrene (1), a protected 4-vinylphenol, leading to poly(4-acetoxystyrene) with well-defined molecular weight and narrow molecular weight distribution was carried out in bulk with a,a'-dibromoxylene(2)/CuBr/2,2-bipyridine(bpy) as initi......Living atom transfer radical polymerization (ATRP) of 4-acetoxystyrene (1), a protected 4-vinylphenol, leading to poly(4-acetoxystyrene) with well-defined molecular weight and narrow molecular weight distribution was carried out in bulk with a,a'-dibromoxylene(2)/CuBr/2,2-bipyridine...

  13. Nonradiative charge transfer in collisions of protons with rubidium atoms

    Institute of Scientific and Technical Information of China (English)

    Yan Ling-Ling; Qu Yi-Zhi; Liu Chun-Hua; Zhang Yu; Wang Jian-Guo; Buenker Robert J

    2012-01-01

    The nonradiative charge-transfer cross sections for protons colliding with Rb(5s) atoms are calculated by using the quantum-mechanical molecularorbital close-coupling method in an energy range of 10-3 keV 10 keV.The total and state-selective charge-transfer cross sections are in good agreement with the experimental data in the relatively low energy region.The importance of rotational coupling for chargetransfer process is stressed.Compared with the radiative charge-transfer process,nonradiative charge transfer is a dominant mechanism at energies above 15 eV.The resonance structures of state-selective charge-transfer cross sections arising from the competition among channels are analysed in detail.The radiative and nonradiative charge-transfer rate coefficients from low to high temperature are presented.

  14. Ultracold, radiative charge transfer in hybrid Yb ion - Rb atom traps

    CERN Document Server

    McLaughlin, B M; Lane, I C; McCann, J F

    2014-01-01

    Ultracold hybrid ion-atom traps offer the possibility of microscopic manipulation of quantum coherences in the gas using the ion as a probe. However, inelastic processes, particularly charge transfer can be a significant process of ion loss and has been measured experimentally for the Yb$^{+}$ ion immersed in a Rb vapour. We use first-principles quantum chemistry codes to obtain the potential energy curves and dipole moments for the lowest-lying energy states of this complex. Calculations for the radiative decay processes cross sections and rate coefficients are presented for the total decay processes. Comparing the semi-classical Langevin approximation with the quantum approach, we find it provides a very good estimate of the background at higher energies. The results demonstrate that radiative decay mechanisms are important over the energy and temperature region considered. In fact, the Langevin process of ion-atom collisions dominates cold ion-atom collisions. For spin dependent processes \\cite{kohl13} the...

  15. Reverse Atom Transfer Radical Polymerization of (-)-Menthyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    The reverse atom transfer radical polymerization(RATRP) of (-)-menthyl methacrylate ((-)-MnMA) with AIBN(AIBN/CuCl2/bipyridine(bipy) or (-)sparteine((-)Sp) =1/2/4) initiating system in THF has been studied. The dependence of the specific rotation on molecular weight was investigated.

  16. Synthesis of Amphiphilic Copolymwers by Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Hansen, Natanya Majbritt Louie

    2007-01-01

    atom transfer radikal polymerisation (ATRP) blev anvendt til alle polymerisationerne. De reaktionskinetiske forhold samt de opnåelige materialestrukturer viste, at næsten alle anvendte monomer-kombinationer kan håndteres til fremstilling af fluorholdige polymermaterialer med velkontrolleret struktur...

  17. Scientometric Dimensions of Innovation Communication Productivity of the Chemistry Division at Bhabha Atomic Research Centre

    OpenAIRE

    Kademani, B.S.; Surwase, Ganesh; Anil Sagar; Lalit Mohan; Gaderao, C. R.; Anil Kumar; Kalyane, V. L.; Prakasan, E.R.; Vijai Kumar

    2005-01-01

    Scientrometric analysis of 1733 papers published by the teams comprising total of 926 participating scientists at Chemistry Division of Bhabha Atomic Research Centre (BARC) during 1970-1999 in the domains: Radiation & Photochemistry and Chemical Dynamics (649), Solid State Studies (558), Inorganic, Structural and Materials Chemistry (460) and Theoretical Chemistry (66) were analysed for yearwise productivity, authorship pattern and collaboration. The highest number of publicationsin a year we...

  18. Atoms-First Curriculum: A Comparison of Student Success in General Chemistry

    Science.gov (United States)

    Esterling, Kevin M.; Bartels, Ludwig

    2013-01-01

    We present an evaluation of the impact of an atoms-first curriculum on student success in introductory chemistry classes and find that initially a lower fraction of students obtain passing grades in the first and second quarters of the general chemistry series. This effect is more than reversed for first-quarter students after one year of…

  19. Atoms-First Curriculum: A Comparison of Student Success in General Chemistry

    Science.gov (United States)

    Esterling, Kevin M.; Bartels, Ludwig

    2013-01-01

    We present an evaluation of the impact of an atoms-first curriculum on student success in introductory chemistry classes and find that initially a lower fraction of students obtain passing grades in the first and second quarters of the general chemistry series. This effect is more than reversed for first-quarter students after one year of…

  20. Synthesis of Novel Chiral Stationary Phase Based on Atom Transfer Radical Polymerization and Click Chemistry%基于原子转移自由基聚合和“Click”化学方法制备手性色谱固定相

    Institute of Scientific and Technical Information of China (English)

    王怀松; 彭江涛; 魏纪平; 姜安

    2012-01-01

    应用原子转移自由基聚合(ATRP)法和“Click”化学方法,以含叠氮基的烯类化合物为单体,在硅胶表面引发聚合,制备了“梳状”手性固定相.该固定相的合成采用“接出”方法接枝聚合物链,使接枝层更为均匀,并且避免了传统合成方法(如物理吸附等)稳定性差的缺点.所得到的“梳状”手性固定相实现了对一些手性药物的分离;并考察了该固定相中聚合物链的密度和长度对其手性分离能力的影响.%A novel chiral stationary phase was synthesized via the combination of atom transfer radical po- lymerization (ATRP) and click chemistry. In the synthesis, the silane coupling agent 3-(2-bromoisobutyryl)- propyl triethoxysilane (BPE) was chosen as the ATRP initiator and immobized on the porous silica gel. The polymer chains of poly(2-methyl-3-butyn-2-ol methacrylate) (pMBMA) were grafted on the silica substrates by surface-initiated ATRP. This "grafting-from" technique was used to synthesize polymers with controlla- ble molecular weight and narrow molecular weight distributions. For immobilizing the chiral selector, azide-modified β-cyclodextrin (β-CD) was synthesized and bounded on the pMBMA by click chemistry, which can avoid the side-reactions in the preparation. The materials with different pMBMA chain density and length on the silica gel surface were prepared. Several pharmaceuticals were used to evaluate the enantioseparation ability of the materials under reversed-phase high performance liquid chromatography. The results demonstrate that ATRP can well design the polymer structure, and click chemistry can provide an ef- fective route in the β-CD immobilization for chiral discrimination. It was found that the retention and separation factors of chiral compounds could be improved by adjusting the pMBMA chain density and length on the surface of silica gel.

  1. Correlated energy transfer between two ultracold atomic species

    Science.gov (United States)

    Krönke, Sven; Knörzer, Johannes; Schmelcher, Peter

    2015-05-01

    We study a single atom as an open quantum system, which is initially prepared in a coherent state of low energy and oscillates in a one-dimensional harmonic trap through an interacting ensemble of NA bosons, held in a displaced trap [arXiv:1410.8676]. The non-equilibrium quantum dynamics of the total system is simulated by means of an ab-initio method, giving us access to all properties of the open system and its finite environment. In this talk, we focus on unraveling the interplay of energy exchange and correlations between the subsystems, which are coupled in such a spatio-temporally localized manner. We show that an inter-species interaction-induced level splitting accelerates the energy transfer between the atomic species for larger NA, which becomes less complete at the same time. System-environment correlations prove to be significant except for times when the excess energy distribution among the subsystems is highly imbalanced. These correlations result in incoherent energy transfer processes, which accelerate the early energy donation of the single atom. By analyzing correlations between intra-subsystem excitations, certain energy transfer channels are shown to be (dis-)favored depending on the instantaneous direction of transfer.

  2. Population transfer via adiabatic passage in the Rydberg potassium atom

    Institute of Scientific and Technical Information of China (English)

    2007-01-01

    Using the time-dependent multilevel approach, we have calculated the coherent population transfer between the quantum states of potassium atom by a single frequency-chirped laser pulse. The result shows that a pair of sequential 'broadband' frequency-chirped laser pulses can efficiently transfer population from the initial state of the ladder system to the target state. It is also found that the population can be efficiently transferred to a target state and trapped there by using an 'intuitive' or a 'counterintuitive' frequency sweep laser pulse in the case of 'narrowband' frequency-chirped laser pulse. Our research shows that the complete population transfer is related to the pulse duration, chirp rate, and amplitude of the laser pulse.

  3. Secondary Students' Mental Models of Atoms and Molecules: Implications for Teaching Chemistry.

    Science.gov (United States)

    Harrison, Allan G.; Treagust, David F.

    1996-01-01

    Examines the reasoning behind views of atoms and molecules held by students (n=48) and investigates how mental models may assist or hamper further instruction in chemistry. Reports that students prefer models of atoms and molecules that depict them as discrete, concrete structures. Recommends that teachers develop student modeling skills and…

  4. Volatile organic compound ratios as probes of halogen atom chemistry in the Arctic

    Directory of Open Access Journals (Sweden)

    P. B. Shepson

    2008-03-01

    Full Text Available Volatile organic compound concentration ratios can be used as indicators of halogen chemistry that occurs during ozone depletion events in the Arctic during spring. Here we use a combination of modeling and measurements of [acetone]/[propanal] as an indicator of bromine chemistry, and [isobutane]/[n-butane] and [methyl ethyl ketone]/[n-butane] are used to study the extent of chlorine chemistry during four ozone depletion events during the Polar Sunrise Experiment of 1995. Using a 0-D photochemistry model in which the input of halogen atoms is controlled and varied, the approximate ratio of [Br]/[Cl] can be estimated for each ozone depletion event. It is concluded that there must be an additional source of propanal (likely from the snowpack to correctly simulate the VOC chemistry of the Arctic, and further evidence that the ratio of Br atoms to Cl atoms can vary greatly during ozone depletion events is presented.

  5. Volatile organic compound ratios as probes of halogen atom chemistry in the Arctic

    Directory of Open Access Journals (Sweden)

    A. E. Cavender

    2007-08-01

    Full Text Available Volatile organic compound concentration ratios can be used as indicators of halogen chemistry that occurs during ozone depletion events in the Arctic during spring. Here we use a combination of modeling and measurements of [acetone]/[propanal] as an indicator of bromine chemistry, and [isobutane]/[n-butane] and [methyl ethyl ketone]/[n-butane] are used to study the extent of chlorine chemistry during four ozone depletion events during the Polar Sunrise Experiment of 1995. Using a 0-D photochemistry model in which the input of halogen atoms is controlled and varied, the approximate ratio of [Br]/[Cl] can be estimated for each ozone depletion event. It is concluded that there must be an additional source of propanal (likely from the snowpack to correctly simulate the VOC chemistry of the Arctic, and that the ratio of Br atoms to Cl atoms can vary greatly during ozone depletion events.

  6. Intrinsic barriers for H-atom transfer reactions involving hydrocarbons

    Energy Technology Data Exchange (ETDEWEB)

    Camaioni, D.M.; Autrey, S.T.; Franz, J.A.

    1994-08-01

    Intrinsic barriers (formally the barrier in the absence of driving force) for H-atom transfer reactions are key parameters in Evans-Polyanyi and Marcus equations for estimating exothermic reaction barriers and are fundamentally significant for the insight they provide about bond reorganization energies for formation of transition state structures. Although knowable from experiment, relatively few of these barriers have been measured due to experimental difficulties in measuring rates for identity reactions. Thus, the authors have used semiempirical Molecular Orbital theoretical methods (MNDO/PM3) to calculate barriers for a series of H-atom transfer identity reactions involving alkyl, alkenyl, arylalkyl and hydroaryl radicals and donors. Briefly stated, they find that barriers decrease with the degree of alkyl substitution at the radical site whereas barriers increase with the degree of conjugation with the radical site. Details of the methodology and analyses of how these barrier heights correlate with reactant and transition state properties will be presented and discussed.

  7. Chemical Principles Revisited: Updating the Atomic Theory in General Chemistry.

    Science.gov (United States)

    Whitman, Mark

    1984-01-01

    Presents a descriptive overview of recent achievements in atomic structure to provide instructors with the background necessary to enhance their classroom presentations. Topics considered include hadrons, quarks, leptons, forces, and the unified fields theory. (JN)

  8. Intrinsic barriers for H-atom transfer reactions

    Energy Technology Data Exchange (ETDEWEB)

    Camaioni, D.M.; Autrey, S.T.; Franz, J.A.

    1994-08-01

    Hydrogen transfer reactions play a well-recognized role in coal liquefaction. While H-abstraction reactions between radicals and H-donors have been well-studied, understanding of structure-reactivity relationships remains surprisingly incomplete. Another form of hydrogen transfer known as radical hydrogen transfer (radical donation of H to an unsaturated compound) is currently the subject of much speculation. The barriers for identity reactions are key parameters in the Evans-Polanyi equation for estimating reaction barriers and are fundamentally significant for the insight they provide about bond reorganization energies for formation of transition state structures. Although knowable from experiment, relatively few H-abstraction identity barriers and no barriers for hydrocarbon radical hydrogen transfer reactions have been measured. This paper seeks to supplement and extend existing experimental data with results obtained by calculation. The authors have used ab initio and semiempirical molecular orbital methods (MNDO-PM3) to calculate barriers for a series of H-atom abstraction and radical-hydrogen-transfer identity reactions for alkyl, alkenyl, arylalkyl and hydroaryl systems. Details of this methodology and analyses of how barrier heights correlate with reactant and transition state properties will be presented and discussed.

  9. Presidential Green Chemistry Challenge: 2009 Academic Award

    Science.gov (United States)

    Presidential Green Chemistry Challenge 2009 award winner, Professor Krzysztof Matyjaszewski, developed Atom Transfer Radical Polymerization to make polymers with copper catalysts and environmentally friendly reducing agents.

  10. Atomic structure and chemistry of human serum albumin

    Science.gov (United States)

    He, Xiao M.; Carter, Daniel C.

    1992-01-01

    The three-dimensional structure of human serum albumin has been determined crystallographically to a resolution of 2.8 A. It comprises three homologous domains that assemble to form a heart-shaped molecule. Each domain is a product of two subdomains that possess common structural motifs. The principal regions of ligand binding to human serum albumin are located in hydrophobic cavities in subdomains IIA and ILIA, which exhibit similar chemistry. The structure explains numerous physical phenomena and should provide insight into future pharmacokinetic and genetically engineered therapeutic applications of serum albumin.

  11. Alkane desaturation by concerted double hydrogen atom transfer to benzyne.

    Science.gov (United States)

    Niu, Dawen; Willoughby, Patrick H; Woods, Brian P; Baire, Beeraiah; Hoye, Thomas R

    2013-09-26

    The removal of two vicinal hydrogen atoms from an alkane to produce an alkene is a challenge for synthetic chemists. In nature, desaturases and acetylenases are adept at achieving this essential oxidative functionalization reaction, for example during the biosynthesis of unsaturated fatty acids, eicosanoids, gibberellins and carotenoids. Alkane-to-alkene conversion almost always involves one or more chemical intermediates in a multistep reaction pathway; these may be either isolable species (such as alcohols or alkyl halides) or reactive intermediates (such as carbocations, alkyl radicals, or σ-alkyl-metal species). Here we report a desaturation reaction of simple, unactivated alkanes that is mechanistically unique. We show that benzynes are capable of the concerted removal of two vicinal hydrogen atoms from a hydrocarbon. The discovery of this exothermic, net redox process was enabled by the simple thermal generation of reactive benzyne intermediates through the hexadehydro-Diels-Alder cycloisomerization reaction of triyne substrates. We are not aware of any single-step, bimolecular reaction in which two hydrogen atoms are simultaneously transferred from a saturated alkane. Computational studies indicate a preferred geometry with eclipsed vicinal C-H bonds in the alkane donor.

  12. Introductory lecture: Time-resolved chemistry at atomic resolution.

    Science.gov (United States)

    Coppens, Philip; Novozhilova, Irina V

    2003-01-01

    Though time-resolved studies are still at an early stage, the field is rapidly being developed and applied to an increasingly broad spectrum of problems with timescales varying from seconds or more down to femtoseconds. In this overview a number of different techniques are discussed, with emphasis on chemical applications in which information is obtained at the atomic level. The need to correlate with theory, both for calibration of theoretical methods and to obtain related information not accessible experimentally, is stressed.

  13. Chemical Structure and Properties: A Modified Atoms-First, One-Semester Introductory Chemistry Course

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Johnson, Brian J.; Jakubowski, Henry V.; McKenna, Anna G.; McIntee, Edward J.; Jones, T. Nicholas; Fazal, M. A.; Peterson, Alicia A.

    2015-01-01

    A one-semester, introductory chemistry course is described that develops a primarily qualitative understanding of structure-property relationships. Starting from an atoms-first approach, the course examines the properties and three-dimensional structure of metallic and ionic solids before expanding into a thorough investigation of molecules. In…

  14. Chemical Structure and Properties: A Modified Atoms-First, One-Semester Introductory Chemistry Course

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Johnson, Brian J.; Jakubowski, Henry V.; McKenna, Anna G.; McIntee, Edward J.; Jones, T. Nicholas; Fazal, M. A.; Peterson, Alicia A.

    2015-01-01

    A one-semester, introductory chemistry course is described that develops a primarily qualitative understanding of structure-property relationships. Starting from an atoms-first approach, the course examines the properties and three-dimensional structure of metallic and ionic solids before expanding into a thorough investigation of molecules. In…

  15. Radiative charge transfer in cold and ultracold Sulfur atoms colliding with Protons

    CERN Document Server

    Shen, G; Wang, J G; McCann, J F; McLaughlin, B M

    2015-01-01

    Radiative decay processes at cold and ultra cold temperatures for Sulfur atoms colliding with protons are investigated. The MOLPRO quantum chemistry suite of codes was used to obtain accurate potential energies and transition dipole moments, as a function of internuclear distance, between low-lying states of the SH$^{+}$ molecular cation. A multi-reference configuration-interaction (MRCI) approximation together with the Davidson correction is used to determine the potential energy curves and transition dipole moments, between the states of interest, where the molecular orbitals (MO's) are obtained from state-averaged multi configuration-self-consistent field (MCSCF) calculations. The collision problem is solved approximately using an optical potential method to obtain radiative loss, and a fully two-channel quantum approach for radiative charge transfer. Cross sections and rate coefficients are determined for the first time for temperatures ranging from 10 $\\mu$ K up to 10,000 K. Results are obtained for all ...

  16. Do Spin State and Spin Density Affect Hydrogen Atom Transfer Reactivity?

    Science.gov (United States)

    Saouma, Caroline T; Mayer, James M

    2014-01-01

    The prevalence of hydrogen atom transfer (HAT) reactions in chemical and biological systems has prompted much interest in establishing and understanding the underlying factors that enable this reactivity. Arguments have been advanced that the electronic spin state of the abstractor and/or the spin-density at the abstracting atom are critical for HAT reactivity. This is consistent with the intuition derived from introductory organic chemistry courses. Herein we present an alternative view on the role of spin state and spin-density in HAT reactions. After a brief introduction, the second section introduces a new and simple fundamental kinetic analysis, which shows that unpaired spin cannot be the dominant effect. The third section examines published computational studies of HAT reactions, which indicates that the spin state affects these reactions indirectly, primarily via changes in driving force. The essay concludes with a broader view of HAT reactivity, including indirect effects of spin and other properties on reactivity. It is suggested that some of the controversy in this area may arise from the diversity of HAT reactions and their overlap with proton-coupled electron transfer (PCET) reactions.

  17. Free Radical Chemistry Enabled by Visible Light-Induced Electron Transfer.

    Science.gov (United States)

    Staveness, Daryl; Bosque, Irene; Stephenson, Corey R J

    2016-10-18

    temperature conditions. Evolving from this work, a new avenue toward atom transfer radical addition (ATRA) chemistry was developed, enabling dual functionalization of both double and triple bonds. Importantly, we have also expanded our portfolio to target clinically relevant scaffolds. Photoredox catalysis proved effective in generating high value fluorinated alkyl radicals through the use of abundantly available starting materials, providing access to libraries of trifluoromethylated (hetero)arenes as well as intriguing gem-difluoro benzyl motifs via a novel photochemical radical Smiles rearrangement. Finally, we discuss a photochemical strategy toward sustainable lignin processing through selective C-O bond cleavage methodology. The collection of these efforts is meant to highlight the potential for visible light-mediated radical chemistry to impact a variety of industrial sectors.

  18. Free Radical Chemistry Enabled by Visible Light-Induced Electron Transfer

    Science.gov (United States)

    2016-01-01

    -mediated, ambient temperature conditions. Evolving from this work, a new avenue toward atom transfer radical addition (ATRA) chemistry was developed, enabling dual functionalization of both double and triple bonds. Importantly, we have also expanded our portfolio to target clinically relevant scaffolds. Photoredox catalysis proved effective in generating high value fluorinated alkyl radicals through the use of abundantly available starting materials, providing access to libraries of trifluoromethylated (hetero)arenes as well as intriguing gem-difluoro benzyl motifs via a novel photochemical radical Smiles rearrangement. Finally, we discuss a photochemical strategy toward sustainable lignin processing through selective C–O bond cleavage methodology. The collection of these efforts is meant to highlight the potential for visible light-mediated radical chemistry to impact a variety of industrial sectors. PMID:27529484

  19. [Electron transfer, ionization, and excitation in atomic collisions]. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    1992-12-31

    Fundamental processes of electron transfer, ionization, and excitation in ion-atom and ion-ion collisions are studied. Attention is focussed on one- and two-electron systems and, more recently, quasi-one-electron systems whose electron-target-ion core can be accurately modeled by one-electron potentials. The basic computational approaches can then be taken with few, if any, approximations, and the underlying collisional mechanisms can be more clearly revealed. At intermediate collision energies (e.g., proton energies for p-He{sup +} collisions on the order of 100 kilo-electron volts), many electronic states are strongly coupled during the collision, a coupled-state approach, such as a coupled-Sturmian-pseudostate approach, is appropriate. At higher collision energies (million electron-volt energies) the coupling is weaker with, however, many more states being coupled together, so that high-order perturbation theory is essential.

  20. Electron transfer, ionization, and excitation in atomic collisions

    Energy Technology Data Exchange (ETDEWEB)

    Winter, T.G.; Alston, S.G.

    1992-01-01

    The research being carried out at Penn State by Winter and Alston addresses the fundamental processes of electron transfer, ionization, and excitation in ion-atom (and ion-ion) collisions. The focus is on intermediate- and higher-energy collisions, corresponding to proton energies of about 25 kilo-electron-volts (keV) or larger. At intermediate energies, where the transition probabilities are not small, many states must be coupled in a large calculation, while at higher energies, perturbative approaches may be used. Several studies have been carried out in the current three-year period; most of these treat systems with only one or two electrons, so that fewer approximations need be made and the basic collisional mechanisms can be more clearly described.

  1. The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

    Science.gov (United States)

    Koontz, Steve L.; Leger, Lubert J.; Wu, Corina; Cross, Jon B.; Jurgensen, Charles W.

    1994-01-01

    Neutral atomic oxygen is the most abundant component of the ionospheric plasma in the low Earth orbit environment (LEO; 200 to 700 kilometers altitude) and can produce significant degradation of some spacecraft materials. In order to produce a more complete understanding of the materials chemistry of atomic oxygen, the chemistry and physics of O-atom interactions with materials were determined in three radically different environments: (1) The Space Shuttle cargo bay in low Earth orbit (the EOIM-3 space flight experiment), (2) a high-velocity neutral atom beam system (HVAB) at Los Alamos National Laboratory (LANL), and (3) a microwave-plasma flowing-discharge system at JSC. The Space Shuttle and the high velocity atom beam systems produce atom-surface collision energies ranging from 0.1 to 7 eV (hyperthermal atoms) under high-vacuum conditions, while the flowing discharge system produces a 0.065 eV surface collision energy at a total pressure of 2 Torr. Data obtained in the three different O-atom environments referred to above show that the rate of O-atom reaction with polymeric materials is strongly dependent on atom kinetic energy, obeying a reactive scattering law which suggests that atom kinetic energy is directly available for overcoming activation barriers in the reaction. General relationships between polymer reactivity with O atoms and polymer composition and molecular structure have been determined. In addition, vacuum ultraviolet photochemical effects have been shown to dominate the reaction of O atoms with fluorocarbon polymers. Finally, studies of the materials chemistry of O atoms have produced results which may be of interest to technologists outside the aerospace industry. Atomic oxygen 'spin-off' or 'dual use' technologies in the areas of anisotropic etching in microelectronic materials and device processing, as well as surface chemistry engineering of porous solid materials are described.

  2. The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

    Science.gov (United States)

    Koontz, Steve L.; Leger, Lubert J.; Wu, Corina; Cross, Jon B.; Jurgensen, Charles W.

    1994-01-01

    Neutral atomic oxygen is the most abundant component of the ionospheric plasma in the low Earth orbit environment (LEO; 200 to 700 kilometers altitude) and can produce significant degradation of some spacecraft materials. In order to produce a more complete understanding of the materials chemistry of atomic oxygen, the chemistry and physics of O-atom interactions with materials were determined in three radically different environments: (1) The Space Shuttle cargo bay in low Earth orbit (the EOIM-3 space flight experiment), (2) a high-velocity neutral atom beam system (HVAB) at Los Alamos National Laboratory (LANL), and (3) a microwave-plasma flowing-discharge system at JSC. The Space Shuttle and the high velocity atom beam systems produce atom-surface collision energies ranging from 0.1 to 7 eV (hyperthermal atoms) under high-vacuum conditions, while the flowing discharge system produces a 0.065 eV surface collision energy at a total pressure of 2 Torr. Data obtained in the three different O-atom environments referred to above show that the rate of O-atom reaction with polymeric materials is strongly dependent on atom kinetic energy, obeying a reactive scattering law which suggests that atom kinetic energy is directly available for overcoming activation barriers in the reaction. General relationships between polymer reactivity with O atoms and polymer composition and molecular structure have been determined. In addition, vacuum ultraviolet photochemical effects have been shown to dominate the reaction of O atoms with fluorocarbon polymers. Finally, studies of the materials chemistry of O atoms have produced results which may be of interest to technologists outside the aerospace industry. Atomic oxygen 'spin-off' or 'dual use' technologies in the areas of anisotropic etching in microelectronic materials and device processing, as well as surface chemistry engineering of porous solid materials are described.

  3. Temperature-dependent kinetics of charge transfer, hydrogen-atom transfer, and hydrogen-atom expulsion in the reaction of CO+ with CH4 and CD4.

    Science.gov (United States)

    Melko, Joshua J; Ard, Shaun G; Johnson, Ryan S; Shuman, Nicholas S; Guo, Hua; Viggiano, Albert A

    2014-09-18

    We have determined the rate constants and branching ratios for the reactions of CO(+) with CH4 and CD4 in a variable-temperature selected ion flow tube. We find that the rate constants are collisional for all temperatures measured (193-700 K for CH4 and 193-500 K for CD4). For the CH4 reaction, three product channels are identified, which include charge transfer (CH4(+) + CO), H-atom transfer (HCO(+) + CH3), and H-atom expulsion (CH3CO(+) + H). H-atom transfer is slightly preferred to charge transfer at low temperature, with the charge-transfer product increasing in contribution as the temperature is increased (H-atom expulsion is a minor product for all temperatures). Analogous products are identified for the CD4 reaction. Density functional calculations on the CO(+) + CH4 reaction were also conducted, revealing that the relative temperature dependences of the charge-transfer and H-atom transfer pathways are consistent with an initial charge transfer followed by proton transfer.

  4. Structure and Chemistry of Atomic Clusters from Supersonic Beams.

    Science.gov (United States)

    Yang, Shi-He.

    A tandem time-of-flight (TOF) apparatus was designed to study the structure and chemistry of cold transition metal cluster ions from supersonic beams. By means of a photodissociation laser fluence dependence technique, binding energies of Nb_{rm x }^{+} (x = 2 - 20), Co_{rm x}^{+ } (x = 4 - 20) and etc. were found to generally increase with cluster size. The desorption energies of Nb_{rm x}N _2^{+} (x = 2 - 17) and Nb_{rm x} CO^{+} (x = 2 - 10) also increase with cluster size with some oscillations similar to the size dependent reactivities of these clusters. Photodetachment studies revealed that electron affinities of copper clusters increase with cluster size with a sharp even/odd alternation. Unlike other noble metals, Ag_{rm x}^ {-} clusters display two competing processes: photodissociation and photodetachment. Relative reactivities of cluster ions of Nb, Co, Ag, and etc. have been measured using a fast flow cluster reactor, displaying a similar function of cluster size to that of the neutrals. In addition, preliminary photoelectron experiments have been performed on Cu_{ rm x}^{-} and Nb _{rm x}^{-}. A magnetic Time-of-flight ultraviolet photoelectron spectrometer (MTOFUPS) has been developed to study electronic structures of cold metal and semiconductor cluster anions prepared in supersonic beams. Application of this spectrometer to carbon clusters with a F_2 laser (7.9 eV) allowed their electron affinities and UPS patterns to be measured,demonstrating a remarkable structural evolution of these clusters: Chains (C_2^{ -}-C_9^{-} ) - Rings (C_{10}^ {-}-C_{29}^ {-}) - Cages (C_{38 }^{-}-C_{84 }^{-}). In particular, the UPS of C_{60}^{-} is in excellent agreement with the CNDO/S calculation, providing a striking spectral evidence for the highly symmetric icosahedral soccer ball structure--Buckminsterfullerene. For comparison, the UPS of Si_ {rm x}^{-} and Ge_{rm x}^{ -} are presented. Unlike carbon clusters which prefer structures of low dimensionality, these

  5. Tape transfer atomization patterning of liquid alloys for microfluidic stretchable wireless power transfer.

    Science.gov (United States)

    Jeong, Seung Hee; Hjort, Klas; Wu, Zhigang

    2015-02-12

    Stretchable electronics offers unsurpassed mechanical compliance on complex or soft surfaces like the human skin and organs. To fully exploit this great advantage, an autonomous system with a self-powered energy source has been sought for. Here, we present a new technology to pattern liquid alloys on soft substrates, targeting at fabrication of a hybrid-integrated power source in microfluidic stretchable electronics. By atomized spraying of a liquid alloy onto a soft surface with a tape transferred adhesive mask, a universal fabrication process is provided for high quality patterns of liquid conductors in a meter scale. With the developed multilayer fabrication technique, a microfluidic stretchable wireless power transfer device with an integrated LED was demonstrated, which could survive cycling between 0% and 25% strain over 1,000 times.

  6. Iodinated (Perfluoro)alkyl Quinoxalines by Atom Transfer Radical Addition Using ortho-Diisocyanoarenes as Radical Acceptors.

    Science.gov (United States)

    Leifert, Dirk; Studer, Armido

    2016-09-12

    A simple method for the preparation of functionalized quinoxalines is reported. Starting from readily accessible ortho-diisocyanoarenes and (perfluoro)alkyl iodides, the quinoxaline core is constructed during (perfluoro)alkylation by atom transfer radical addition (ATRA), resulting in 2-iodo-3-(perfluoro)alkylquinoxalines. The radical cascades are readily initiated either with visible light or by using α,α'-azobisisobutyronitrile (AIBN). The heteroarene products are obtained in high yields (up to 94 %), and the method can be readily scaled up. Useful follow-up chemistry documents the value of the novel radical quinoxaline synthesis.

  7. Chemistry of the heaviest elements--one atom at a time

    Energy Technology Data Exchange (ETDEWEB)

    Hoffman, Darleane C.; Lee, Diana M.

    2000-01-01

    In keeping with the goal of the Viewpoint series of the Journal of Chemical Education, this article gives a 75-year perspective of the chemistry of the heaviest elements, including a 50-year retrospective view of past developments, a summary of current research achievements and applications, and some predictions about exciting, new developments that might be envisioned within the next 25 years. A historical perspective of the importance of chemical separations in the discoveries of the transuranium elements from neptunium (Z=93) through mendelevium (Z=101) is given. The development of techniques for studying the chemical properties of mendelevium and still heavier elements on the basis of measuring the radioactive decay of a single atom (''atom-at-a-time'' chemistry) and combining the results of many separate experiments is reviewed. The influence of relativistic effects (expected to increase as Z{sup 2}) on chemical properties is discussed. The results from recent atom-at-a-time studies of the chemistry of the heaviest elements through seaborgium (Z=106) are summarized and show that their properties cannot be readily predicted based on simple extrapolation from the properties of their lighter homologues in the periodic table. The prospects for extending chemical studies to still heavier elements than seaborgium are considered and appear promising.

  8. Atomic Scale Imaging of the Electronic Structure and Chemistry of Graphene and Its Precursors on Metal Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Flynn, George W [Columbia University

    2015-02-16

    atom, provides information about the electronic structure of graphene and is particularly sensitive to the sign and magnitude of the charge transfer between graphene and any surface adsorbed species. Results: (A) Graphene on SiO2 In an effort designed to unravel aspects of the mechanisms for chemistry on graphene surfaces, STM and STS were employed to show that graphene on SiO2 is oxidized at lower temperatures than either graphite or multi-layer graphene. Two independent factors control this charge transfer: (1) the degree of graphene coupling to the substrate, and (2) exposure to oxygen and moisture. (B) Graphene on Copper In the case of graphene grown on copper surfaces, we found that the graphene grows primarily in registry with the underlying copper lattice for both Cu(111) and Cu(100). On Cu(111) the graphene has a hexagonal superstructure with a significant electronic component, whereas it has a linear superstructure on Cu(100). (C) Nitrogen Doped Graphene on Copper Using STM we have also studied the electronic structure and morphology of graphene films grown on a copper foil substrate in which N atoms substitute for carbon in the 2-D graphene lattice. The salient features of the results of this study were: (1) Nitrogen doped graphene on Cu foil exhibits a triangular structure with an “apparent” slight elevation of ~ 0.8 Å at N atom substitution sites; (2) Nitrogen doping results in ~0.4 electrons per N atom donated to the graphene lattice; (3) Typical N doping of graphene on Cu foil shows mostly single site Carbon atom displacement (~ 3N/1000C); (4) Some multi-site C atom displacement is observed (<10% of single site events). (D) Boron Doped Graphene on Copper We also used scanning tunneling microscopy and x-ray spectroscopy to characterize the atomic and electronic structure of boron-doped graphene created by chemical vapor deposition on copper substrates. Microscopic measurements show that boron, like nitrogen, incorporates into the carbon lattice

  9. Faster oxygen atom transfer catalysis with a tungsten dioxo complex than with its molybdenum analog.

    Science.gov (United States)

    Arumuganathan, T; Mayilmurugan, Ramasamy; Volpe, Manuel; Mösch-Zanetti, Nadia C

    2011-08-21

    The synthesis and characterization of a series of molybdenum ([MoO(2)Cl(L(n))]; L(1) (1), L(2) (3)) and tungsten ([WO(2)Cl(L(n))]; L(1) (2), L(2) (4)) dioxo complexes (L(1) = 1-methyl-4-(2-hydroxybenzyl)-1,4-diazepane and L(2) = 1-methyl-4-(2-hydroxy-3,5-di-tert-butylbenzyl)-1,4-diazepane) of tridentate aminomonophenolate ligands HL(1) and HL(2) are reported. The ligands were obtained by reductive amination of 1-methyl-1,4-diazepane with the corresponding aldehyde. Complexes 3 and 4 were obtained by the reaction of [MO(2)Cl(2)(dme)(n)] (M = Mo, n = 0; W, n = 1) with the corresponding ligand in presence of a base, whereas for the preparation of 1 and 2 the ligands were deprotonated by KH prior to the addition to the metal. They were characterized by NMR and IR spectroscopy, by cyclic voltammetry, mass spectrometry, elemental analysis and by single-crystal X-ray diffraction analysis. Solid-state structures of the molybdenum and tungsten cis-dioxo complexes reveal hexa-coordinate metal centers surrounded by two oxo groups, a chloride ligand and by the tridentate monophenolate ligand which coordinates meridionally through its [ONN] donor set. In the series of compounds 1-4, complexes 3 and 4 have been used as catalysts for the oxygen atom transfer reaction between dimethyl sulfoxide (DMSO) and trimethyl phosphine (PMe(3)). Surprisingly, faster oxygen atom transfer (OAT) reactivity has been observed for the tungsten complex [WO(2)Cl(L(2))] (4) in comparison to its molybdenum analog [MoO(2)Cl(L(2))] (3) at room temperature. The kinetic results are discussed and compared in terms of their reactivity. This journal is © The Royal Society of Chemistry 2011

  10. Quantum Diffusion-Controlled Chemistry: Reactions of Atomic Hydrogen with Nitric Oxide in Solid Parahydrogen.

    Science.gov (United States)

    Ruzi, Mahmut; Anderson, David T

    2015-12-17

    Our group has been working to develop parahydrogen (pH2) matrix isolation spectroscopy as a method to study low-temperature condensed-phase reactions of atomic hydrogen with various reaction partners. Guided by the well-defined studies of cold atom chemistry in rare-gas solids, the special properties of quantum hosts such as solid pH2 afford new opportunities to study the analogous chemical reactions under quantum diffusion conditions in hopes of discovering new types of chemical reaction mechanisms. In this study, we present Fourier transform infrared spectroscopic studies of the 193 nm photoinduced chemistry of nitric oxide (NO) isolated in solid pH2 over the 1.8 to 4.3 K temperature range. Upon short-term in situ irradiation the NO readily undergoes photolysis to yield HNO, NOH, NH, NH3, H2O, and H atoms. We map the postphotolysis reactions of mobile H atoms with NO and document first-order growth in HNO and NOH reaction products for up to 5 h after photolysis. We perform three experiments at 4.3 K and one at 1.8 K to permit the temperature dependence of the reaction kinetics to be quantified. We observe Arrhenius-type behavior with a pre-exponential factor of A = 0.036(2) min(-1) and Ea = 2.39(1) cm(-1). This is in sharp contrast to previous H atom reactions we have studied in solid pH2 that display definitively non-Arrhenius behavior. The contrasting temperature dependence measured for the H + NO reaction is likely related to the details of H atom quantum diffusion in solid pH2 and deserves further study.

  11. How in Spite of the Rhetoric, History of Chemistry Has Been Ignored in Presenting Atomic Structure in Textbooks.

    Science.gov (United States)

    Rodriguez, Maria A.; Niaz, Mansoor

    2002-01-01

    Reports on a study designed to: (a) show how the importance of the history of chemistry has been recognized in the classroom; (b) demonstrate how criteria based on history and philosophy of science can be used to evaluate the presentation of atomic structure in general chemistry textbooks; and (c) compare new (1970-1992) and old textbooks…

  12. How in Spite of the Rhetoric, History of Chemistry Has Been Ignored in Presenting Atomic Structure in Textbooks.

    Science.gov (United States)

    Rodriguez, Maria A.; Niaz, Mansoor

    2002-01-01

    Reports on a study designed to: (a) show how the importance of the history of chemistry has been recognized in the classroom; (b) demonstrate how criteria based on history and philosophy of science can be used to evaluate the presentation of atomic structure in general chemistry textbooks; and (c) compare new (1970-1992) and old textbooks…

  13. Momentum Transfer of an Atom Moving in an Optical Cavity

    Institute of Scientific and Technical Information of China (English)

    张敬涛; 徐至展

    2001-01-01

    When an atom moves in an optical cavity, the total momentum of the atom does not remain constant. We study a two-level atom moving slowly in an optical cavity, and give the time dependence of its mean momentum. It is found that when the initial momentum of the atom is larger than that of the photon, the mean momentum oscillates around a value less than the initial value. But, if the initial momentum is less than the momentum of the photon, the mean momentum of the atom is greater than its initial value in most cases.

  14. Effects of delocalization on intrinsic barriers for H-atom transfer: Implications for the radical hydrogen transfer reaction

    Energy Technology Data Exchange (ETDEWEB)

    Camaioni, D.M.; Autrey, S.T.; Ferris, K.F.; Franz, J.A.

    1992-08-01

    PM3 calculations of transition states (TS) for both normal H-atom transfer and radical hydrogen transfer (RHT) reactions of a a wide-variety of hydrocarbon structures have enabled development of quantitative structure-reactivity relationships. Results indicate that activation barriers for RHT reactions are large enough that thermoneutral and endothermic reactions should not compete with alternative multistep pathways.

  15. Why has the bohr-sommerfeld model of the atom been ignoredby general chemistry textbooks?

    Science.gov (United States)

    Niaz, Mansoor; Cardellini, Liberato

    2011-12-01

    Bohr's model of the atom is considered to be important by general chemistry textbooks. A major shortcoming of this model was that it could not explain the spectra of atoms containing more than one electron. In order to increase the explanatory power of the model, Sommerfeld hypothesized the existence of elliptical orbits. This study has the following objectives: 1) Formulation of criteria based on a history and philosophy of science framework; and 2) Evaluation of university-level general chemistry textbooks based on the criteria, published in Italy and U.S.A. Presentation of a textbook was considered to be "satisfactory" if it included a description of the Bohr-Sommerfeld model along with diagrams of the elliptical orbits. Of the 28 textbooks published in Italy that were analyzed, only five were classified as "satisfactory". Of the 46 textbooks published in U.S.A., only three were classified as "satisfactory". This study has the following educational implications: a) Sommerfeld's innovation (auxiliary hypothesis) by introducing elliptical orbits, helped to restore the viability of Bohr's model; b) Bohr-Sommerfeld's model went no further than the alkali metals, which led scientists to look for other models; c) This clearly shows that scientific models are tentative in nature; d) Textbook authors and chemistry teachers do not consider the tentative nature of scientific knowledge to be important; e) Inclusion of the Bohr-Sommerfeld model in textbooks can help our students to understand how science progresses.

  16. Continuously transferring cold atoms in caesium double magneto-optical trap

    Institute of Scientific and Technical Information of China (English)

    Yan Shu-Bin; Geng Tao; Zhang Tian-Cai; Wang Jun-Min

    2006-01-01

    We have established a caesium double magneto-optical trap (MOT) system for cavity-QED experiment, and demonstrated the continuous transfer of cold caesium atoms from the vapour-cell MOT with a pressure of ~ 1 × 10-6 Pa to the ultra-high-vacuum (UHV) MOT with a pressure of ~ 8 × 10-8 Pa via a focused continuous-wave transfer laser beam. The effect of frequency detuning as well as the intensity of the transfer beam is systematically investigated, which makes the transverse cooling adequate before the atoms leak out of the vapour-cell MOT to reduce divergence of the cold atomic beam. The typical cold atomic flux got from vapour-cell MOT is ~ 2 × 107 atoms/s. About 5 × 106 caesium atoms are recaptured in the UHV MOT.

  17. The relationship between recollection, knowledge transfer, and student attitudes towards chemistry

    Science.gov (United States)

    Odeleye, Oluwatobi Omobonike

    Certain foundational concepts, including acid-base theory, chemical bonding and intermolecular forces (IMFs), appear throughout the undergraduate chemistry curriculum. The level of understanding of these foundational concepts influences the ability of students to recognize the relationships between sub-disciplines in chemistry. The purpose of this study was to investigate the relationship between student attitudes towards chemistry and their abilities to recollect and transfer knowledge of IMFs, a foundational concept, to their daily lives as well as to other classes. Data were collected using surveys, interviews and classroom observations, and analyzed using qualitative methods. The data show that while most students were able to function at lower levels of thinking by providing a definition of IMFs, majority were unable to function at higher levels of thinking as evidenced by their inability to apply their knowledge of IMFs to their daily lives and other classes. The results of this study suggest a positive relationship between students' abilities to recollect knowledge and their abilities to transfer that knowledge. The results also suggest positive relationships between recollection abilities of students and their attitudes towards chemistry as well as their transfer abilities and attitudes towards chemistry. Recommendations from this study include modifications of pedagogical techniques in ways that facilitate higher-level thinking and emphasize how chemistry applies not only to daily life, but also to other courses.

  18. Introduction of the Scientific Method and Atomic Theory to Liberal Arts Chemistry Students

    Science.gov (United States)

    Hohman, James R.

    1998-12-01

    Liberal arts chemistry students often struggle with the application of the scientific method to problem solving in the sciences, in part because of insufficient concrete examples. These same students also tend to have significant difficulty in appreciating the value of weight ratios in chemistry, particularly in the establishment of the laws that led to the atomic theory. A simple classroom exercise utilizing net weights of envelopes containing varying numbers of BB's or paper clips can be used to illustrate and differentiate the steps of the scientific method: observation (with corrections) to get scientific facts, induction to arrive at laws, tentative explanation by hypothesis, experimentation to test the hypothesis, and final establishment of a scientific theory. Since the students participating in this exercise arrive at each of these steps on their own, there is greater appreciation and more effective internalization of the scientific method on their part. The exercise depends upon the discrete nature of the BB's or paper clips (i.e., on the fact that they are individual "particles" of similar properties, and so are useful analogies to atoms). Finally, since weight ratios are used to solve the problem posed by this exercise, it can be used to lead directly into the weight ratios summarized by the laws of constant composition (fixed proportions) and multiple proportions, which in turn lead to Dalton's atomic theory.

  19. Demystifying Introductory Chemistry. Part 4: An Approach to Reaction Thermodynamics through Enthalpies, Entropies, and Free Energies of Atomization.

    Science.gov (United States)

    Spencer, James N.; And Others

    1996-01-01

    Presents an alternative approach to teaching reaction thermodynamics in introductory chemistry courses using calculations of enthalpies, entropies, and free energies of atomization. Uses a consistent concept, that of decomposition of a compound to its gaseous atoms, to discuss not only thermodynamic parameters but also equilibrium and…

  20. Using an Advanced Computational Laboratory Experiment to Extend and Deepen Physical Chemistry Students' Understanding of Atomic Structure

    Science.gov (United States)

    Hoffman, Gary G.

    2015-01-01

    A computational laboratory experiment is described, which involves the advanced study of an atomic system. The students use concepts and techniques typically covered in a physical chemistry course but extend those concepts and techniques to more complex situations. The students get a chance to explore the study of atomic states and perform…

  1. A scheme for transferring an unknown atomic entangled state via cavity quantum electrodynamics

    Institute of Scientific and Technical Information of China (English)

    Wu Tao; Ye Liu; Ni Zhi-Xiang

    2006-01-01

    In this paper, we propose a scheme for transferring an unknown atomic entangled state via cavity quantum electrodynamics (QED). This scheme, which has a successful probability of 100 percent, does not require Bell-state measurement and performing any operations to reconstruct an initial state. Meanwhile, the scheme only involves atomfield interaction with a large detuning and does not require the transfer of quantum information between the atoms and cavity. Thus the scheme is insensitive to the cavity field states and cavity decay. This scheme can also be extended to transfer ring an entangled state of n-atom.

  2. Antioxidant Activity/Capacity Measurement. 2. Hydrogen Atom Transfer (HAT)-Based, Mixed-Mode (Electron Transfer (ET)/HAT), and Lipid Peroxidation Assays.

    Science.gov (United States)

    Apak, Reşat; Özyürek, Mustafa; Güçlü, Kubilay; Çapanoğlu, Esra

    2016-02-10

    Measuring the antioxidant activity/capacity levels of food extracts and biological fluids is useful for determining the nutritional value of foodstuffs and for the diagnosis, treatment, and follow-up of numerous oxidative stress-related diseases. Biologically, antioxidants play their health-beneficial roles via transferring a hydrogen (H) atom or an electron (e(-)) to reactive species, thereby deactivating them. Antioxidant activity assays imitate this action; that is, antioxidants are measured by their H atom transfer (HAT) or e(-) transfer (ET) to probe molecules. Antioxidant activity/capacity can be monitored by a wide variety of assays with different mechanisms, including HAT, ET, and mixed-mode (ET/HAT) assays, generally without distinct boundaries between them. Understanding the principal mechanisms, advantages, and disadvantages of the measurement assays is important for proper selection of method for valid evaluation of antioxidant properties in desired applications. This work provides a general and up-to-date overview of HAT-based, mixed-mode (ET/HAT), and lipid peroxidation assays available for measuring antioxidant activity/capacity and the chemistry behind them, including a critical evaluation of their advantages and drawbacks.

  3. Synthesis and characterization of poly(2-ethylhexyl acrylate) prepared via atom transfer radical polymerization, reverse atom transfer radical polymerization and radical polymerization

    Indian Academy of Sciences (India)

    Dhruba Jyoti Haloi; Bishnu Prasad Koiry; Prithwiraj Mandal; Nikhil Kumar Singha

    2013-07-01

    This investigation reports a comparative study of poly(2-ethylhexyl acrylate) (PEHA) prepared via atom transfer radical polymerization (ATRP), reverse atom transfer radical polymerization (RATRP) and conventional free radical polymerization (FRP). The molecular weights and the molecular weight distributions of the polymers were measured by gel permeation chromatography (GPC) analysis. Structural characterization of the polymers was carried out by 1H NMR and MALDI-TOF-MS analyses. Thermal properties of the polymers were evaluated by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The polymerization results and the thermal properties of PEHAs prepared via ATRP, RATRP and FRP were compared.

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

    Science.gov (United States)

    Bull, Barbara Jeanne

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

  5. Schwinger variational calculation of ionization of hydrogen atoms for large momentum transfers

    Indian Academy of Sciences (India)

    K Chakrabarti

    2002-03-01

    Schwinger variational principle is used here to study large momentum transfer cases of electron and positron impact ionization of atomic hydrogen from the ground state at intermediate and moderately high energies. The results appear somewhat better compared to other theories.

  6. Mesoscale effects in electrochemical conversion: coupling of chemistry to atomic- and nanoscale structure in iron-based electrodes.

    Science.gov (United States)

    Wiaderek, Kamila M; Borkiewicz, Olaf J; Pereira, Nathalie; Ilavsky, Jan; Amatucci, Glenn G; Chupas, Peter J; Chapman, Karena W

    2014-04-30

    The complex coupling of atomic, chemical, and electronic transformations across multiple length scales underlies the performance of electrochemical energy storage devices. Here, the coupling of chemistry with atomic- and nanoscale structure in iron conversion electrodes is resolved by combining pair distribution function (PDF) and small-angle X-ray scattering (SAXS) analysis for a series of Fe fluorides, oxyfluorides, and oxides. The data show that the anion chemistry of the initial electrode influences the abundance of atomic defects in the Fe atomic lattice. This, in turn, is linked to different atom mobilities and propensity for particle growth. Competitive nanoparticle growth in mixed anion systems contributes to a distinct nanostructure, without the interconnected metallic nanoparticles formed for single anion systems.

  7. Transferring orbital and spin angular momenta of light to atoms

    Energy Technology Data Exchange (ETDEWEB)

    Picon, A; Benseny, A; Mompart, J [Departament de Fisica, Universitat Autonoma de Barcelona, E-08193 Bellaterra (Spain); Vazquez de Aldana, J R; Plaja, L [Servicio Laser, Universidad de Salamanca, E-37008 Salamanca (Spain); Calvo, G F [Mathematics Department and IMACI-Institute of Applied Mathematics in Science and Engineering, Universidad de Castilla-La Mancha, E-13071 Ciudad Real (Spain); Roso, L, E-mail: antonio.picon@uab.ca [Centro de Laseres Pulsados, CLPU, Patio de Escuelas 1, E-37008 Salamanca (Spain)

    2010-08-15

    Light beams carrying orbital angular momentum (OAM), such as Laguerre-Gaussian (LG) beams, give rise to the violation of the standard dipolar selection rules during interaction with matter, yielding, in general, an exchange of angular momentum larger than {h_bar} per absorbed photon. By means of ab initio three-dimensional (3D) numerical simulations, we investigate in detail the interaction of a hydrogen atom with intense Gaussian and LG light pulses. We analyze the dependence of the angular momentum exchange with the polarization, the OAM and the carrier-envelope phase of light, as well as with the relative position between the atom and the light vortex. In addition, a quantum-trajectory approach based on the de Broglie-Bohm formulation of quantum mechanics is used to gain physical insight into the absorption of angular momentum by the hydrogen atom.

  8. The pentafluorostyrene endeavours with atom transfer radical polymerization - quo vadis?

    DEFF Research Database (Denmark)

    Hvilsted, Søren

    2014-01-01

    by exploitation of the very labile para-fluorine demonstrates new material architecture possibilities through very mild reaction conditions. Finally the utility of PFS in various conducting materials is elaborated. The amphiphilic nature of PFS in triblock copolymers with polyethers has been exploited for Li+ ion...... electrolytes. The convenient grafting of PFS through ‘click’ chemistry to a polysulfone and subsequent phosphonation of the PFS grafts seem very beneficial for the fabrication of proton conducting materials with high conductivity...

  9. Insights into the Hydrogen-Atom Transfer of the Blue Aroxyl.

    Science.gov (United States)

    Bächle, Josua; Marković, Marijana; Kelterer, Anne-Marie; Grampp, Günter

    2017-07-26

    An experimental and theoretical study on hydrogen-atom transfer dynamics in the hydrogen-bonded substituted phenol/phenoxyl complex of the blue aroxyl (2,4,6-tri-tert-butylphenoxyl) is presented. The experimental exchange dynamics is determined in different organic solvents from the temperature-dependent alternating line-width effect in the continuous-wave ESR spectrum. From bent Arrhenius plots, effective tunnelling contributions with parallel heavy-atom motion are concluded. To clarify the transfer mechanism, reaction paths for different conformers of the substituted phenol/phenoxyl complex are modelled theoretically. Various DFT and post-Hartree-Fock methods including multireference methods are applied. From the comparison of experimental and theoretical data it is concluded that the system favours concerted hydrogen-atom transfer along a parabolic reaction path caused by heavy-atom motion. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Coherent population transfer in Rydberg potassium atom by a single frequency-chirped laser pulse

    Institute of Scientific and Technical Information of China (English)

    Zhang Xian-Zhou; Ma Qiao-Zhi; Li Xiao-Hong

    2006-01-01

    By using the time-dependent multilevel approach, we have calculated the coherent population transfer among the quantum states of potassium atom by a single frequency-chirped laser pulse. The results show that the population can be efficiently transferred to a target state and be trapped there by using an ‘intuitive’ or a ‘counter-intuitive’ frequency sweep laser pulse in the case of ‘narrowband’ frequency-chirped laser pulse. It is also found that a pair of sequential ‘broadband’ frequency-chirped laser pulses can efficiently transfer population from one ground state of the A atom to the other one.

  11. Radical and Atom Transfer Halogenation (RATH): A Facile Route for Chemical and Polymer Functionalization.

    Science.gov (United States)

    Han, Yi-Jen; Lin, Chia-Yu; Liang, Mong; Liu, Ying-Ling

    2016-05-01

    This work demonstrates a new halogenation reaction through sequential radical and halogen transfer reactions, named as "radical and atom transfer halogenation" (RATH). Both benzoxazine compounds and poly(2,6-dimethyl-1,4-phenylene oxide) have been demonstrated as active species for RATH. Consequently, the halogenated compound becomes an active initiator of atom transfer radical polymerization. Combination of RATH and sequential ATRP provides an convenient and effective approach to prepare reactive and crosslinkable polymers. The RATH reaction opens a new window both to chemical synthesis and molecular design and preparation of polymeric materials.

  12. Entanglement and quantum state transfer between two atoms trapped in two indirectly coupled cavities

    Science.gov (United States)

    Zheng, Bin; Shen, Li-Tuo; Chen, Ming-Feng

    2016-05-01

    We propose a one-step scheme for implementing entanglement generation and the quantum state transfer between two atomic qubits trapped in two different cavities that are not directly coupled to each other. The process is realized through engineering an effective asymmetric X-Y interaction for the two atoms involved in the gate operation and an auxiliary atom trapped in an intermediate cavity, induced by virtually manipulating the atomic excited states and photons. We study the validity of the scheme as well as the influences of the dissipation by numerical simulation and demonstrate that it is robust against decoherence.

  13. Efficient scheme for entangled states and quantum information transfer with trapped atoms in a resonator

    Institute of Scientific and Technical Information of China (English)

    Li Peng-Bo; Li Fu-Li

    2011-01-01

    A protocol is proposed to generate atomic entangled states and implement quantum information transfer in a cavity quantum electrodynamics system. It utilizes Raman transitions or stimulated Raman adiabatic passages between two systems to entangle the ground states of two three-state A-type atoms trapped in a single mode cavity. It does not need the measurements on cavity field nor atomic detection and can be implemented in a deterministic fashion. Since the present protocol is insensitive to both cavity decay and atomic spontaneous emission,it may have some interesting applications in quantum information processing.

  14. Excitation and charge transfer in low-energy hydrogen atom collisions with neutral atoms: Theory, comparisons, and application to Ca

    CERN Document Server

    Barklem, Paul S

    2016-01-01

    A theoretical method for the estimation of cross sections and rates for excitation and charge transfer processes in low-energy hydrogen atom collisions with neutral atoms, based on an asymptotic two-electron model of ionic-covalent interactions in the neutral atom-hydrogen atom system, is presented. The calculation of potentials and non-adiabatic radial couplings using the method is demonstrated. The potentials are used together with the multi-channel Landau-Zener model to calculate cross sections and rate coefficients. The main feature of the method is that it employs asymptotically exact atomic wavefunctions, which can be determined from known atomic parameters. The method is applied to Li+H, Na+H, and Mg+H collisions, and the results compare well with existing detailed full-quantum calculations. The method is applied to the astrophysically important problem of Ca+H collisions, and rate coefficients are calculated for temperatures in the range 1000-20000 K.

  15. Nitrogen Atom Transfer From High Valent Iron Nitrides

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, Michael D. [New Mexico State Univ., Las Cruces, NM (United States); Smith, Jeremy M. [Indiana Univ., Bloomington, IN (United States)

    2015-10-14

    This report describes the synthesis and reactions of high valent iron nitrides. Organonitrogen compounds such as aziridines are useful species for organic synthesis, but there are few efficient methods for their synthesis. Using iron nitrides to catalytically access these species may allow for their synthesis in an energy-and atom-efficient manner. We have developed a new ligand framework to achieve these goals as well as providing a method for inducing previously unknown reactivity.

  16. Chemical Exchange Saturation Transfer (CEST) Agents: Quantum Chemistry and MRI.

    Science.gov (United States)

    Li, Jikun; Feng, Xinxin; Zhu, Wei; Oskolkov, Nikita; Zhou, Tianhui; Kim, Boo Kyung; Baig, Noman; McMahon, Michael T; Oldfield, Eric

    2016-01-04

    Diamagnetic chemical exchange saturation transfer (CEST) contrast agents offer an alternative to Gd(3+) -based contrast agents for MRI. They are characterized by containing protons that can rapidly exchange with water and it is advantageous to have these protons resonate in a spectral window that is far removed from water. Herein, we report the first results of DFT calculations of the (1) H nuclear magnetic shieldings in 41 CEST agents, finding that the experimental shifts can be well predicted (R(2) =0.882). We tested a subset of compounds with the best MRI properties for toxicity and for activity as uncouplers, then obtained mice kidney CEST MRI images for three of the most promising leads finding 16 (2,4-dihydroxybenzoic acid) to be one of the most promising CEST MRI contrast agents to date. Overall, the results are of interest since they show that (1) H NMR shifts for CEST agents-charged species-can be well predicted, and that several leads have low toxicity and yield good in vivo MR images.

  17. Thermal chemistry of copper acetamidinate atomic layer deposition precursors on silicon oxide surfaces studied by XPS

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Yunxi; Zaera, Francisco, E-mail: zaera@ucr.edu [Department of Chemistry, University of California, Riverside, California 92521 (United States)

    2016-01-15

    The thermal surface chemistry of copper(I)-N,N′-di-sec-butylacetamidinate, [Cu({sup s}Bu-amd)]{sub 2}, a metalorganic complex recently proposed for the chemical-based deposition of copper films, has been characterized on SiO{sub 2} films under ultrahigh vacuum conditions by x-ray photoelectron spectroscopy (XPS). Initial adsorption at cryogenic temperatures results in the oxidation of the copper centers with Cu 2p{sub 3/2} XPS binding energies close to those seen for a +2 oxidation state, an observation that the authors interpret as the result of the additional coordination of oxygen atoms from the surface to the Cu atoms of the molecular acetamidinate dimer. Either heating to 300 K or dosing the precursor directly at that temperature leads to the loss of one of its two ligands, presumably via hydrogenation/protonation with a hydrogen/proton from a silanol group, or following a similar reaction on a defect site. By approximately 500 K the Cu 2p{sub 3/2}, C 1s, and N 1s XPS data suggest that the remaining acetamidinate ligand is displaced from the copper center and bonds to the silicon oxide directly, after which temperatures above 900 K need to be reached to promote further (and only partial) decomposition of those organic moieties. It was also shown that the uptake of the Cu precursor is self-limiting at either 300 or 500 K, although the initial chemistry is somewhat different at the two temperatures, and that the nature of the substrate also defines reactivity, with the thin native silicon oxide layer always present on Si(100) surfaces being less reactive than thicker films grown by evaporation, presumably because of the lower density of surface nucleation sites.

  18. A quasi-classical study of energy transfer in collisions of hyperthermal H atoms with SO2 molecules

    Science.gov (United States)

    da Silva, Ramon S.; Garrido, Juan D.; Ballester, Maikel Y.

    2017-08-01

    A deep understanding of energy transfer processes in molecular collisions is at central attention in physical chemistry. Particularly vibrational excitation of small molecules colliding with hot light atoms, via a metastable complex formation, has shown to be an efficient manner of enhancing reactivity. A quasi-classical trajectory study of translation-to-vibration energy transfer (T-V ET) in collisions of hyperthermal H(2S) atoms with SO2(X˜ 1A') molecules is presented here. For such a study, a double many-body expansion potential energy surface previously reported for HSO2(2A) is used. This work was motivated by recent experiments by Ma et al. studying collisions of H + SO2 at the translational energy of 59 kcal/mol [J. Ma et al., Phys. Rev. A 93, 040702 (2016)]. Calculations reproduce the experimental evidence that during majority of inelastic non-reactive collision processes, there is a metastable intermediate formation (HOSO or HSO2). Nevertheless, the analysis of the trajectories shows that there are two distinct mechanisms in the T-V ET process: direct and indirect. Direct T-V processes are responsible for the high population of SO2 with relatively low vibrational excitation energy, while indirect ones dominate the conversion from translational energy to high values of the vibrational counterpart.

  19. Angular-momentum transfer due to postcollision interaction in atomic inner n s2 -shell photoionization

    Science.gov (United States)

    Gerchikov, L.; Guillemin, R.; Simon, M.; Sheinerman, S.

    2017-06-01

    A concrete mechanism of angular-momentum transfer in photoionization process is proposed for electron photoemission from deep inner atomic shells. It is demonstrated that the leading contribution to angular-momentum transfer is provided by postcollision interaction of the photoelectrons and Auger electrons. The standard theoretical approach to postcollision interaction has been considerably improved by taking into account angular-momentum transfer. The theory developed is applied to the photoionization of 1 s2 shell in Ar. Calculations show the noticeable influence of angular-momentum transfer on the photoelectron angular distribution.

  20. Population transfer by femtosecond laser pulses in a ladder-type atomic system

    Institute of Scientific and Technical Information of China (English)

    Fan Xi-Jun; Li Ai-Yun; Tong Dian-Min; Liu Cheng-Pu

    2008-01-01

    The population transfer in a ladder-type atomic system driven by linearly polarized sech-shape femtosecond laser pulses is investigated by numerically solving Schrodinger equation without including the rotating wave approximation (RWA). It is shown that population transfer is mainly determined by the Rabi frequency (strength) of the driving laser field and the chirp rate, and that the ratio of the dipole moments and the pulse width also have a prominent effect on the population transfer. By choosing appropriate values of the above parameters, complete population transfer can be realized.

  1. Use of a PhET Interactive Simulation in General Chemistry Laboratory: Models of the Hydrogen Atom

    Science.gov (United States)

    Clark, Ted M.; Chamberlain, Julia M.

    2014-01-01

    An activity supporting the PhET interactive simulation, Models of the Hydrogen Atom, has been designed and used in the laboratory portion of a general chemistry course. This article describes the framework used to successfully accomplish implementation on a large scale. The activity guides students through a comparison and analysis of the six…

  2. The Use of Gas Chromatography and Mass Spectrometry to Introduce General Chemistry Students to Percent Mass and Atomic Mass Calculations

    Science.gov (United States)

    Pfennig, Brian W.; Schaefer, Amy K.

    2011-01-01

    A general chemistry laboratory experiment is described that introduces students to instrumental analysis using gas chromatography-mass spectrometry (GC-MS), while simultaneously reinforcing the concepts of mass percent and the calculation of atomic mass. Working in small groups, students use the GC to separate and quantify the percent composition…

  3. Use of a PhET Interactive Simulation in General Chemistry Laboratory: Models of the Hydrogen Atom

    Science.gov (United States)

    Clark, Ted M.; Chamberlain, Julia M.

    2014-01-01

    An activity supporting the PhET interactive simulation, Models of the Hydrogen Atom, has been designed and used in the laboratory portion of a general chemistry course. This article describes the framework used to successfully accomplish implementation on a large scale. The activity guides students through a comparison and analysis of the six…

  4. The Use of Gas Chromatography and Mass Spectrometry to Introduce General Chemistry Students to Percent Mass and Atomic Mass Calculations

    Science.gov (United States)

    Pfennig, Brian W.; Schaefer, Amy K.

    2011-01-01

    A general chemistry laboratory experiment is described that introduces students to instrumental analysis using gas chromatography-mass spectrometry (GC-MS), while simultaneously reinforcing the concepts of mass percent and the calculation of atomic mass. Working in small groups, students use the GC to separate and quantify the percent composition…

  5. Correlation Between Energy Transfer Rate and Atomization Energy of Some Trinitro Aromatic Explosive Molecules

    Institute of Scientific and Technical Information of China (English)

    Su-hong Ge; Xin-lu Cheng; Zheng-lai Liu; Xiang-dong Yang; Fang-fang Dong

    2008-01-01

    An assumptive theoretical relationship is suggested to describe the property of molecular atomization energy and energy transfer rate in the initiation of explosions. To investigate the relationship between atomization energy and energy transfer rate, the number of doorway modes of explosives is estimated by the theory of Dlott and Fayer in which the rate is proportional to the number of normal mode vibrations. It was evaluated frequencies of normal mode vibrations of eight molecules by means of density functional theory (DFT) at the b3p86/6-31G(d,p) level. It is found that the number of doorway modes shows a linear correlation to the atomization energies of the molecules, which were also calculated by means of the same method. A mechanism of this correlation is discussed. It is also noted that in those explosives with similar molecular structure and molecular weight, the correlation between the atomization energy and the number of doorway modes is higher.

  6. Quantum state transfer and logic gates with two 3-level atoms in cavity QED

    Science.gov (United States)

    Yang, Chui-Ping; Chu, Shih-I.

    2004-08-01

    We present a new way to implement quantum controlled phase-shift gate, quantum exchange gate (SWAP gate), and quantum state transfer with two 3-level atoms in cavity QED. The method does not involve real excitation of a cavity photon during the operation, thus decoherence induced due to the cavity-photon decay is minimized. In addition, it is remarkable that for all present purposes, no auxiliary atoms or any measurement is needed. Therefore, the operation is significantly simplified.

  7. Reactions of substituted benzene anions with N and O atoms: Chemistry in Titan's upper atmosphere and the interstellar medium

    Science.gov (United States)

    Wang, Zhe-Chen; Bierbaum, Veronica M.

    2016-06-01

    The likely existence of aromatic anions in many important extraterrestrial environments, from the atmosphere of Titan to the interstellar medium (ISM), is attracting increasing attention. Nitrogen and oxygen atoms are also widely observed in the ISM and in the ionospheres of planets and moons. In the current work, we extend previous studies to explore the reactivity of prototypical aromatic anions (deprotonated toluene, aniline, and phenol) with N and O atoms both experimentally and computationally. The benzyl and anilinide anions both exhibit slow associative electron detachment (AED) processes with N atom, and moderate reactivity with O atom in which AED dominates but ionic products are also formed. The reactivity of phenoxide is dramatically different; there is no measurable reaction with N atom, and the moderate reactivity with O atom produces almost exclusively ionic products. The reaction mechanisms are studied theoretically by employing density functional theory calculations, and spin conversion is found to be critical for understanding some product distributions. This work provides insight into the rich gas-phase chemistry of aromatic ion-atom reactions and their relevance to ionospheric and interstellar chemistry.

  8. Atomic capture and transfer of negative pions stopped in binary mixtures of hydrogen with polyatomic gases

    Energy Technology Data Exchange (ETDEWEB)

    Vasilyev, V.A.; Levay, B.; Minkova, A.; Petrukhin, V.I.; Horvath, D.

    1985-12-01

    The atomic capture and transfer of stopped negative pions have been studied in binary gas mixtures of H/sub 2/+M, where M is CCl/sub 2/F/sub 2/, CClF/sub 3/, CBrF/sub 3/ or SF/sub 6/. The ..pi../sup 0/ yield, versus relative atomic concentration Csub(A) of M, goes through a maximum at Csub(A)proportional0.1 and levels off at zero at high concentrations. This phenomenon together with other observed characteristics of the atomic capture and transfer of pions in these systems is interpreted in the frame of a phenomenological model. The average transfer coefficients anti ..lambda..sub(Z) exhibit a weak concentration dependence. The estimated average atomic capture ratios anti A(Z/H) are lower than those found for noble gases, probably because of the mutual screening of the constituent atoms in the molecules. The probability of pion capture in an atomic orbit is not proportional to the stopping power of the components of the mixture. (orig.).

  9. Modulation Transfer Spectroscopy of Ytterbium Atoms in a Hollow Cathode Lamp

    Institute of Scientific and Technical Information of China (English)

    WANG Wen-Li; XU Xin-Ye

    2011-01-01

    We present the experimental study of modulation transfer spectroscopy of ytterbium atoms in a hollow cathode lamp.The dependences of its linewidth, slope and magnitude on the various experimental parameters are measured and fitted by the well-known theoretical expressions. The experimental results are in good agreement with the theoretical prediction. We have observed the Dicke narrowing effect by increasing the current of the hollow cathode lamp. It is also found that there are the optimal current and laser power to generate the better modulation transfer spectroscopy signal, which can be employed for locking the laser frequency to the atomic transition.

  10. Atom Transfer Radical Addition to Unactivated Alkenes Employing Heterogeneous Visible Light Photocatalysis.

    Science.gov (United States)

    Mao, Liang-Liang; Cong, Huan

    2017-09-09

    Heterogeneous visible light photocatalysis represents an important direction toward the development of sustainable organic synthesis. In this Communication, we report visible light-induced, heavy metal-free atom transfer radical addition to unactivated terminal olefins using the combination of heterogeneous titanium dioxide as photocatalyst and a hypervalent iodine(III) reagent as co-initiator. The reaction can be applied to a range of substrates with good functional group tolerance under very mild condition. In addition to a number of commonly used atom transfer reagents, the relatively challenging chloroform is also suitable. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Generation of a cold pulsed beam of Rb atoms by transfer from a 3D magneto-optic trap

    CERN Document Server

    Chanu, Sapam Ranjita; Natarajan, Vasant

    2016-01-01

    We demonstrate a technique for producing a cold pulsed beam of atoms by transferring a cloud of atoms trapped in a three dimensional magneto-optic trap (MOT). The MOT is loaded by heating a getter source of Rb atoms. We show that it is advantageous to transfer with two beams (with a small angle between them) compared to a single beam, because the atoms stop interacting with the beams in the two-beam technique, which results in a Gaussian velocity distribution. The atoms are further cooled in optical molasses by turning off the MOT magnetic field before the transfer beams are turned on.

  12. The marriage of metallacycle transfer chemistry with Suzuki-Miyaura cross-coupling to give main group element-containing conjugated polymers.

    Science.gov (United States)

    He, Gang; Kang, Le; Torres Delgado, William; Shynkaruk, Olena; Ferguson, Michael J; McDonald, Robert; Rivard, Eric

    2013-04-10

    A versatile and general synthetic route for the synthesis of conjugated main group element-based polymers, previously inaccessible by conventional means, is reported. These polymers contain five-membered chalcogenophene rings based on S, Se, and Te, and we demonstrate that optoelectronic properties can be readily tuned via controlled atom substitution chemistry. In addition, regioregular hybrid thiophene-selenophene-tellurophene and selenophene-fluorene copolymers were synthesized to provide a further illustration of the scope of the presented metallacycle transfer/cross-coupling polymerization method.

  13. Fast adiabatic quantum state transfer and entanglement generation between two atoms via dressed states

    Science.gov (United States)

    Wu, Jin-Lei; Ji, Xin; Zhang, Shou

    2017-01-01

    We propose a dressed-state scheme to achieve shortcuts to adiabaticity in atom-cavity quantum electrodynamics for speeding up adiabatic two-atom quantum state transfer and maximum entanglement generation. Compared with stimulated Raman adiabatic passage, the dressed-state scheme greatly shortens the operation time in a non-adiabatic way. By means of some numerical simulations, we determine the parameters which can guarantee the feasibility and efficiency both in theory and experiment. Besides, numerical simulations also show the scheme is robust against the variations in the parameters, atomic spontaneous emissions and the photon leakages from the cavity.

  14. Effect of energy transfer from atomic electron shell to an α particle emitted by decaying nucleus

    Energy Technology Data Exchange (ETDEWEB)

    Igashov, S. Yu., E-mail: igashov@theor.mephi.ru [All-Russian Research Institute of Automatics (Russian Federation); Tchuvil’sky, Yu. M. [Moscow State University, Skobeltsyn Institute of Nuclear Physics (Russian Federation)

    2016-12-15

    The process of energy transfer from the electron shell of an atom to an α particle propagating through the shell is formulated mathematically. Using the decay of the {sup 226}Ra nucleus as an example, it is demonstrated that this phenomenon increases the α-decay intensity in contrast with other known effects of similar type. Moreover, the α decay of the nucleus is more strongly affected by the energy transfer than by all other effects taken together.

  15. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing, E-mail: shisq@nwu.edu.cn; Gong, Yongkuan

    2016-11-15

    Highlights: • Biomimetic surface modification of PP was successfully conducted by integrating mussel-inspired technology, thiol chemistry and cell outer membranes-like structures. • The resultant biomimetic surface exhibits good interface and surface stability. • The obvious suppression of protein adsorption and platelet adhesion is also achieved. • The residue thoil groups on the surface could be further functionalized. - Abstract: Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH{sub 2}) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such

  16. Cation-modulated electron-transfer channel: H-atom transfer vs proton-coupled electron transfer with a variable electron-transfer channel in acylamide units.

    Science.gov (United States)

    Chen, Xiaohua; Bu, Yuxiang

    2007-08-08

    The mechanism of proton transfer (PT)/electron transfer (ET) in acylamide units was explored theoretically using density functional theory in a representative model (a cyclic coupling mode between formamide and the N-dehydrogenated formamidic radical, FF). In FF, PT/ET normally occurs via a seven-center cyclic proton-coupled electron transfer (PCET) mechanism with a N-->N PT and an O-->O ET. However, when different hydrated metal ions are bound to the two oxygen sites of FF, the PT/ET mechanism may significantly change. In addition to their inhibition of PT/ET rate, the hydrated metal ions can effectively regulate the FF PT/ET cooperative mechanism to produce a single pathway hydrogen atom transfer (HAT) or a flexible proton coupled electron transfer (PCET) mechanism by changing the ET channel. The regulation essentially originates from the change in the O...O bond strength in the transition state, subject to the binding ability of the hydrated metal ions. In general, the high valent metal ions and those with large binding energies can promote HAT, and the low valent metal ions and those with small binding energies favor PCET. Hydration may reduce the Lewis acidity of cations, and thus favor PCET. Good correlations among the binding energies, barrier heights, spin density distributions, O...O contacts, and hydrated metal ion properties have been found, which can be used to interpret the transition in the PT/ET mechanism. These findings regarding the modulation of the PT/ET pathway via hydrated metal ions may provide useful information for a greater understanding of PT/ET cooperative mechanisms, and a possible method for switching conductance in nanoelectronic devices.

  17. Biomimetic surface modification of polypropylene by surface chain transfer reaction based on mussel-inspired adhesion technology and thiol chemistry

    Science.gov (United States)

    Niu, Zhijun; Zhao, Yang; Sun, Wei; Shi, Suqing; Gong, Yongkuan

    2016-11-01

    Biomimetic surface modification of polypropylene (PP) is conducted by surface chain transfer reaction based on the mussel-inspired versatile adhesion technology and thiol chemistry, using 2-methacryloyloxyethylphosphorylcholine (MPC) as a hydrophilic monomer mimicking the cell outer membrane structure and 2,2-azobisisobutyronitrile (AIBN) as initiator in ethanol. A layer of polydopamine (PDA) is firstly deposited onto PP surface, which not only offers good interfacial adhesion with PP, but also supplies secondary reaction sites (-NH2) to covalently anchor thiol groups onto PP surface. Then the radical chain transfer to surface-bonded thiol groups and surface re-initiated polymerization of MPC lead to the formation of a thin layer of polymer brush (PMPC) with cell outer membrane mimetic structure on PP surface. X-ray photoelectron spectrophotometer (XPS), atomic force microscopy (AFM) and water contact angle measurements are used to characterize the PP surfaces before and after modification. The protein adsorption and platelet adhesion experiments are also employed to evaluate the interactions of PP surface with biomolecules. The results show that PMPC is successfully grafted onto PP surface. In comparison with bare PP, the resultant PP-PMPC surface exhibits greatly improved protein and platelet resistance performance, which is the contribution of both increased surface hydrophilicity and zwitterionic structure. More importantly, the residue thiol groups on PP-PMPC surface create a new pathway to further functionalize such zwitterion modified PP surface.

  18. Auto transfer to Rydberg states during ion-atom collisions

    Energy Technology Data Exchange (ETDEWEB)

    Bachau, H.; Harel, C. (Laboratoire des Collisions Atomiques, Unite Propre de Recherche 260 du CNRS, Universite Bordeaux I, 351 Cours de la Liberation, 33405 Talence (France)); Barat, M.; Roncin, P. (Laboratoire des Collisions Atomiques et Moleculaires, Unite associee 281 du CNRS, Universite de Paris Sud, Batiment 351, 91405 Orsay (France)); Bordenave-Montesquieu, A.; Moretto-Capelle, P.; Benoit-Cattin, P.; Gleizes, A.; Benhenni, M. (IRSAMC, Unite associee 770 du CNRS, Universite Paul Sabatier, 118 route de Narbonne, 31062 Toulouse (France))

    1993-06-05

    Electron capture by slow multiply charged ions colliding on rare-gas targets is known to populate highly excited states of the projectile. On the basis of experimental measurement of energy and angle differential cross-sections we have shown that capture to a resonant doubly excited state may lead to Autoionizing Double Capture (ADC) as well as to True Double Capture (TDC). In this model TDC appears as a two step post-collisional process, the state populated by the collision decays to (or delutes into) a dense adjacent Rydberg series, followed by radiative deexcitation of the inner electron of the (3,n) Rydberg states. We report here new experimental observations in electron spectra measured in [ital N][sup 7+]+[ital He]. Auto transfer to Rydber states has also important consequences on the determination of the lifetime of the autoionizing states, some discrepancies between theoretical width values for low [ital N][sup 5+](4,4) resonant states will be discussed and partially resolved.

  19. Effect of the nature of the substrate on the surface chemistry of atomic layer deposition precursors

    Science.gov (United States)

    Yao, Yunxi; Coyle, Jason P.; Barry, Seán T.; Zaera, Francisco

    2017-02-01

    The thermal chemistry of Cu(I)-sec-butyl-2-iminopyrrolidinate, a promising copper amidinate complex for atomic layer deposition (ALD) applications, was explored comparatively on several surfaces by using a combination of surface-sensitive techniques, specifically temperature-programmed desorption and x-ray photoelectron spectroscopy (XPS). The substrates explored include single crystals of transition metals (Ni(110) and Cu(110)), thin oxide films (NiO/Ni(110) and SiO2/Ta), and oxygen-treated metals (O/Cu(110)). Decomposition of the pyrrolidinate ligand leads to the desorption of several gas-phase products, including CH3CN, HCN and butene from the metals and CO and CO2 from the oxygen-containing surfaces. In all cases dehydrogenation of the organic moieties is accompanied by hydrogen removal from the surface, in the form of H2 on metals and mainly as water from the metal oxides, but the threshold for this chemistry varies wildly, from 270 K on Ni(110) to 430 K on O/Cu(110), 470 K on Cu(110), 500 K on NiO/Ni(110), and 570 K on SiO2/Ta. Copper reduction is also observed in both the Cu 2p3/2 XPS and the Cu L3 VV Auger (AES) spectra, reaching completion by 300 K on Ni(110) but occurring only between 500 and 600 K on Cu(110). On NiO/Ni(110), both Cu(I) and Cu(0) coexist between 200 and 500 K, and on SiO2/Ta a change happens between 500 and 600 K but the reduction is limited, with the copper atoms retaining a significant ionic character. Additional experiments to test adsorption at higher temperatures led to the identification of temperature windows for the self-limiting precursor uptake required for ALD between approximately 300 and 450 K on both Ni(110) and NiO/Ni(110); the range on SiO2 had been previously determined to be wider, reaching an upper limit at about 500 K. Finally, deposition of copper metal films via ALD cycles with O2 as the co-reactant was successfully accomplished on the Ni(110) substrate.

  20. Polymer coating comprising 2-methoxyethyl acrylate units synthesized by surface-initiated atom transfer radical polymerization

    DEFF Research Database (Denmark)

    2011-01-01

    Source: US2012184029A The present invention relates to preparation of a polymer coating comprising or consisting of polymer chains comprising or consisting of units of 2-methoxyethyl acrylate synthesized by Surface-Initiated Atom Transfer Radical Polymerization (SI ATRP) such as ARGET SI ATRP...... or AGET SI ATRP and uses of said polymer coating....

  1. Hydrophilization of poly(ether ether ketone) films by surface-initiated atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren

    2010-01-01

    Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP) has been exploited to hydrophilize PEEK. The ketone groups on the PEEK surface were reduced to hydroxyl groups which were converted to bromoisobutyrate initiating sites for SI-ATRP. The modification steps were followed by contact...

  2. Novel fluorinated block copolymer architectures fuelled by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Jankova, Katja; Hvilsted, Søren

    2005-01-01

    Block copolymers based on poly(pentafluorostyrene), PFS, in various numbers and of different lengths, and polystyrene are prepared by atom transfer radical polymerization (ATRP). Di- and triblock copolymers with varying amounts of PFS were synthesized employing either I phenylethylbromide or 1,4-...

  3. Acrylamide Homopolymers and Acrylamide-N-Isopropylacrylamide Block Copolymers by Atomic Transfer Radical Polymerization in Water

    NARCIS (Netherlands)

    Wever, D. A. Z.; Raffa, P.; Picchioni, F.; Broekhuis, A. A.

    2012-01-01

    Atomic transfer radical polymerization (ATRP) of acrylamide has been accomplished in aqueous media at room temperature. By using methyl 2-chloropropionate (MeClPr) as the initiator and tris[2-(dimethylamino)ethyl]-amine (Me6TREN)/copper halogenide (CuX) as the catalyst system, different linear

  4. Surface-Initiated Atom Transfer Radical Polymerization from Electrospun Mats: An Alternative to Nafion

    DEFF Research Database (Denmark)

    Javakhishvili, Irakli; Dimitrov, Ivaylo; Tynelius, Oskar

    2017-01-01

    Proton exchange membranes for fuel cell applications are synthesized by surface-initiated(SI) atom transfer radical polymerization (ATRP). Poly(vinylidene fluoride-co-chlorotrifluoroethylene)is electrospun into 50 μm thick mat, which is then employed as multifunctionalinitiator for copper...

  5. Acrylamide Homopolymers and Acrylamide-N-Isopropylacrylamide Block Copolymers by Atomic Transfer Radical Polymerization in Water

    NARCIS (Netherlands)

    Wever, D. A. Z.; Raffa, P.; Picchioni, F.; Broekhuis, A. A.

    2012-01-01

    Atomic transfer radical polymerization (ATRP) of acrylamide has been accomplished in aqueous media at room temperature. By using methyl 2-chloropropionate (MeClPr) as the initiator and tris[2-(dimethylamino)ethyl]-amine (Me6TREN)/copper halogenide (CuX) as the catalyst system, different linear polya

  6. Laboratory Measurements of Charge Transfer on Atomic Hydrogen at Thermal Energies

    Science.gov (United States)

    Havener, C. C.; Vane, C. R.; Krause, H. F.; Stancil, P. C.; Mroczkowski, T.; Savin, D. W.

    2002-01-01

    We describe our ongoing program to measure velocity dependent charge transfer (CT) cross sections for selected ions on atomic hydrogen using the ion-aloin merged-beams apparatus at Oak Ridge Natioiial Laboralory. Our focus is on those ions for which CT plays an important role in determining the ionization structure, line emis sion, and thermal structure of observed cosmic photoionized plasmas.

  7. Effect of atomic transfer on the decay of a Bose-Einstein condensate

    CERN Document Server

    Zin, P; Charzynski, S; Herschbach, N; Tol, P; Hogervorst, W; Vassen, W; Zin, Pawel; Dragan, Andrzej; Charzynski, Szymon; Herschbach, Norbert; Tol, Paul; Hogervorst, Wim; Vassen, Wim

    2003-01-01

    We present a model describing the decay of a Bose-Einstein condensate, which assumes the system to remain in thermal equilibrium during the decay. We show that under this assumption transfer of atoms occurs from the condensate to the thermal cloud enhancing the condensate decay rate.

  8. Proton-Conducting Sulfonated Ionomers by Chemical Modification and Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Nielsen, Mads Møller

    of hydrocarbon macromolecular architectures, PSU with postsulfonated polystyrene (PS) grafts are investigated. Here, IEC is controlled through the degree of substitution, the graft length and DS. The grafting is performed with atom transfer radical polymerization (ATRP). The third assessment is dedicated...

  9. Hydrolysis of 4-Acetoxystyrene Polymers Prepared by Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Chen, Xianyi; Jankova, Katja; Kops, Jørgen

    1999-01-01

    Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization was carried out under various reaction conditions. It was found that hydrazinolysis of 4-acetoxystyrene homopolymers, random and block copolymers with styrene in 1,4-dioxane, afforded the corresponding narrow...

  10. Protein repellent hydrophilic grafts prepared by surface-initiated atom transfer radical polymerization from polypropylene

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Eskimergen, Rüya

    2012-01-01

    Grafting of poly(ethylene glycol)methacrylate (PEGMA) and N,N-dimethylacrylamide (DMAAm) from UV-initiator modified polypropylene (PP) was performed by Surface-Initiated Atom Transfer Radical Polymerization (SI-ATRP). The modification and hydrophilization of the PP substrates were confirmed...

  11. Surface-initiated Atom Transfer Radical Polymerization - a Technique to Develop Biofunctional Coatings

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Jankova Atanasova, Katja; Hvilsted, Søren

    2009-01-01

    The initial formation of initiating sites for atom transfer radical polymerization (ATRP) on various polymer surfaces and numerous inorganic and metallic surfaces is elaborated. The subsequent ATRP grafting of a multitude of monomers from such surfaces to generate thin covalently linked polymer...

  12. Near-resonant versus nonresonant chemiluminescent charge-transfer reactions of atomic ions with HCl

    Science.gov (United States)

    Glenewinkel-Meyer, Th.; Ottinger, Ch.

    1994-01-01

    Charge-transfer reactions of C+, O+, F+, Ar+ and some other atomic ions with hydrogen chloride were investigated at collision energies between eVc.m.. This may be due to formation of a long-lived collision complex (Ar-HCl)+.

  13. Muon transfer from muonic hydrogen to heavier atoms; Transfert de charge muonique

    Energy Technology Data Exchange (ETDEWEB)

    Dupays, A

    2004-06-01

    This work concerns muon transfer from muonic hydrogen to heavier atoms. Recently, a method of measurement of the hyperfine structure of ground-state muonic hydrogen based on the collision energy dependence of the muon transfer rate to oxygen has been proposed. This proposal is based on measurements which where performed at the Paul Scherrer Institute in the early nineties which indicate that the muon transfer from muonic hydrogen to oxygen increases by a factor of 4 going from thermal to 0.12 eV energies. The motivation of our calculations was to confirm this behaviour. To study the collision energy dependence of the muon transfer rate, we have used a time-independent close-coupling method. We have set up an hyperspherical elliptic formalism valid for nonzero total angular momentum which allows accurate computations of state-to-state reactive and charge exchange processes. We have applied this formalism to muon-transfer process to oxygen and neon. The comparison with experimental results is in both cases excellent. Finally, the neon transfer rate dependence with energy suggests to use neon instead of oxygen to perform a measurement of the hyperfine structure of muonic hydrogen. The results of accurate calculations of the muon transfer rates from muonic protium and deuterium atoms to nitrogen, oxygen and neon are also reported. Very good agreement with measured rates is obtained and for the three systems, the isotopic effect is perfectly reproduced. (author)

  14. Hydrogen atom transfer reactions in thiophenol: photogeneration of two new thione isomers.

    Science.gov (United States)

    Reva, Igor; Nowak, Maciej J; Lapinski, Leszek; Fausto, Rui

    2015-02-21

    Photoisomerization reactions of monomeric thiophenol have been investigated for the compound isolated in low-temperature argon matrices. The initial thiophenol population consists exclusively of the thermodynamically most stable thiol form. Phototransformations were induced by irradiation of the matrices with narrowband tunable UV light. Irradiation at λ > 290 nm did not induce any changes in isolated thiophenol molecules. Upon irradiation at 290-285 nm, the initial thiol form of thiophenol converted into its thione isomer, cyclohexa-2,4-diene-1-thione. This conversion occurs by transfer of an H atom from the SH group to a carbon atom at the ortho position of the ring. Subsequent irradiation at longer wavelengths (300-427 nm) demonstrated that this UV-induced hydrogen-atom transfer is photoreversible. Moreover, upon irradiation at 400-425 nm, the cyclohexa-2,4-diene-1-thione product converts, by transfer of a hydrogen atom from the ortho to para position, into another thione isomer, cyclohexa-2,5-diene-1-thione. The latter thione isomer is also photoreactive and is consumed if irradiated at λ atom-transfer isomerization reactions dominate the unimolecular photochemistry of thiophenol confined in a solid argon matrix. A set of low-intensity infrared bands, observed in the spectra of UV irradiated thiophenol, indicates the presence of a phenylthiyl radical with an H- atom detached from the SH group. Alongside the H-atom-transfer and H-atom-detachment processes, the ring-opening photoreaction occurred in cyclohexa-2,4-diene-1-thione by the cleavage of the C-C bond at the alpha position with respect to the thiocarbonyl C[double bond, length as m-dash]S group. The resulting open-ring conjugated thioketene adopts several isomeric forms, differing by orientations around single and double bonds. The species photogenerated upon UV irradiation of thiophenol were identified by comparison of their experimental infrared spectra with the spectra theoretically calculated for

  15. Plasma—Particle Transfer Process with Phase—Change and Chemistry Effects

    Institute of Scientific and Technical Information of China (English)

    WangBoyi; TianWendong; 等

    1998-01-01

    A numerical model is proposed to analyze mass,momentum,and energy transfer between plasma and particles in d.c.arc-heated and confined-jet reactors at atmospheric pressure.It emphasizes the phase change and thermal chemistry of particles and includes some other effects such as flow turbulence,gas compressibility and temperature-dependence of the transport properties under the plasma condition Example calculations for plasma-dissociated zirocn process indicate the influences of reactor operation parameters on the plasma jet and particle behavior.

  16. Oxygen atom transfer to a half-sandwich iridium complex: clean oxidation yielding a molecular product.

    Science.gov (United States)

    Turlington, Christopher R; White, Peter S; Brookhart, Maurice; Templeton, Joseph L

    2014-03-12

    The oxidation of [Ir(Cp*)(phpy)(NCAr(F))][B(Ar(F))4] (1; Cp* = η(5)-pentamethylcyclopentadienyl, phpy = 2-phenylene-κC(1')-pyridine-κN, NCAr(F) = 3,5-bis(trifluoromethyl)benzonitrile, B(Ar(F))4 = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) with the oxygen atom transfer (OAT) reagent 2-tert-butylsulfonyliodosobenzene (sPhIO) yielded a single, molecular product at -40 °C. New Ir(Cp*) complexes with bidentate ligands derived by oxidation of phpy were synthesized to model possible products resulting from oxygen atom insertion into the iridium-carbon and/or iridium-nitrogen bonds of phpy. These new ligands were either cleaved from iridium by water or formed unreactive, phenoxide-bridged iridium dimers. The reactivity of these molecules suggested possible decomposition pathways of Ir(Cp*)-based water oxidation catalysts with bidentate ligands that are susceptible to oxidation. Monitoring the [Ir(Cp*)(phpy)(NCAr(F))](+) oxidation reaction by low-temperature NMR techniques revealed that the reaction involved two separate OAT events. An intermediate was detected, synthesized independently with trapping ligands, and characterized. The first oxidation step involves direct attack of the sPhIO oxidant on the carbon of the coordinated nitrile ligand. Oxygen atom transfer to carbon, followed by insertion into the iridium-carbon bond of phpy, formed a coordinated organic amide. A second oxygen atom transfer generated an unidentified iridium species (the "oxidized complex"). In the presence of triphenylphosphine, the "oxidized complex" proved capable of transferring one oxygen atom to phosphine, generating phosphine oxide and forming an Ir-PPh3 adduct in 92% yield. The final Ir-PPh3 product was fully characterized.

  17. Hydrophilization of Poly(ether ether ketone) Films by Surface-initiated Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Eskimergen, Rüya; Burkrinsky, J.T.

    2008-01-01

    -modified PEEK using Surface-Initiated Atom Transfer Radical Polymerization (SI ATRP). Surface reduction of PEEK to form hydroxyl groups [1, 2, 3] was .performed prior to the attachment of 2-bromoisobutyrate initiating groups. Each modification step of PEEK as well as the polymer grafting was followed...... and confirmed by ATR FTIR, water contact ang;le, and Thermal Gravimetric Analysis (TGA). The surface topography was evaluated by "Atomic Force Microscopy (AFM). X-ray Photoelectron Spectroscopy (XPS) has been used to investigate the degree of functionalization. The performed modification allowed for successful...

  18. The diffusion transfer of sputtered atoms in plasma spraying on the internal cylindrical surface

    Energy Technology Data Exchange (ETDEWEB)

    Bondarenko, G.G. [Moscow State University of Electronics and Mathematics, Moscow (Russian Federation); Bonk, O.G.; Kristya, V.I. [Kaluga Branch of N.E. Bauman Moscow University of Technology, Moscow (Russian Federation)

    2001-07-01

    The sputtering of the surface of the solid by the glow discharge plasma is used widely in the electronics for the deposition of thin films. The sputtered atoms (SA), leaving the surface, clash with the gas atoms and the granules the energy. It is interesting to examine the effect of the condensation coefficient of the SA on the concentration of the SA in the cylindrical discharge volume and the fluxes of the SA to different areas of the wall. The solution of this problem for the case of the diffusion transfer of the SA is the subject of this work.

  19. Atom Interferometry with up to 24-Photon-Momentum-Transfer Beam Splitters

    CERN Document Server

    Mueller, Holger; Long, Quan; Herrmann, Sven; Chu, Steven

    2007-01-01

    We present multi- (up to 24-)photon Bragg diffraction as beam splitter to achieve the largest splitting in momentum space in any light-pulse atom interferometer thus far. Relative to the 2-photon processes used in the most sensitive present interferometers, these large momentum transfer beam splitters increase the phase shift 12-fold for Mach-Zehnder and 144-fold for Ramsey-Borde geometries. As the atom's internal state is not changed, important systematic effects can cancel. This dramatic increase in sensitivity and precision opens the door to improved measurements of the fine-structure constant, inertial forces, and tests of relativity and quantum electrodynamics.

  20. Hydrophilization of Poly(ether ether ketone) Films by Surface-initiated Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Fristrup, Charlotte Juel; Eskimergen, Rüya; Burkrinsky, J.T.

    2008-01-01

    -modified PEEK using Surface-Initiated Atom Transfer Radical Polymerization (SI ATRP). Surface reduction of PEEK to form hydroxyl groups [1, 2, 3] was .performed prior to the attachment of 2-bromoisobutyrate initiating groups. Each modification step of PEEK as well as the polymer grafting was followed...... and confirmed by ATR FTIR, water contact ang;le, and Thermal Gravimetric Analysis (TGA). The surface topography was evaluated by "Atomic Force Microscopy (AFM). X-ray Photoelectron Spectroscopy (XPS) has been used to investigate the degree of functionalization. The performed modification allowed for successful...

  1. First Year Chemistry Laboratory Courses for Distance Learners: Development and Transfer Credit Acceptance

    Directory of Open Access Journals (Sweden)

    Sharon E. Brewer,

    2013-07-01

    Full Text Available In delivering chemistry courses by distance, a key challenge is to offer the learner an authentic and meaningful laboratory experience that still provides the rigour required to continue on in science. To satisfy this need, two distance general chemistry laboratory courses appropriate for Bachelor of Science (B.Sc. students, including chemistry majors, have been recently developed at Thompson Rivers University. A constructive alignment process was employed which clearly mapped learning outcomes and activities to appropriate assessment tools. These blended laboratory courses feature custom, home experimental kits and combine elements of online and hands-on learning. The courses were designed for flexible continuous enrollment and provide online resources including tutor support, instructional videos, lab report submission, and student evaluation. The assessment of students includes laboratory reports, safety quizzes, reflective journaling, digital photo documentation, and invigilated written and online practical exams. Emphasizing the quality and rigour in these distance laboratory learning experiences allowed both courses to be accepted for B.Sc. transfer credit by other institutions, an important criterion for students. This paper will outline the design and development process of these new blended laboratory courses, their course structures and assessments, and initial student results.

  2. I. Measuring and Reducing Stress and Surface Roughness in IBAD MgO Films and II. Developing Tools to Measure Transfer in Undergraduate Chemistry Students

    Science.gov (United States)

    Antonakos, Cory Dale

    I. MgO may be grown with a biaxial texture onto an amorphous substrate with the use of ion beam assisted deposition (IBAD). This MgO film may then be used as a platform on which to grow epitaxial films on an amorphous membrane for characterization purposes. However, the IBAD MgO film is stressed, causing buckles in the amorphous membrane and problems with further film growth on the IBAD MgO. This dissertation work explores the source of this film stress and develops methods to relax the stress and reduce surface roughness with annealing and increased growth temperature. It is determined that annealing and increased growth temperature coupled with a higher ion-to-atom ratio (IAR) during film growth reduce stress and surface roughness sufficiently to use even thinner IBAD MgO films as an intermediate layer between an amorphous membrane and epitaxial film. II. Much of the existing literature on knowledge transfer concludes that transfer is rare and does not occur spontaneously. However, studies supporting that transfer is rare often use methods that focus on binary success or failure to solve a problem correctly and do not analyze thought process. This dissertation work aims at developing transfer questions that allow open-ended responses, developing a method of analysis for these responses that looks for transfer in the problem-solving process, and assessing the methodology itself and its sensitivity, validity, and utility as a general transfer measurement technique for use across a broad range of expertise levels in chemistry. Detailed analysis of responses to each transfer question show that some transfer questions are more effective at distinguishing between expertise levels while also allowing responders of all levels to show knowledge transfer. Simpler questions that are more accessible to students of introductory chemistry proved the most useful at eliciting a range of responses that correlate with expertise level while still showing some degree of transfer in

  3. Aqueous reactive species induced by a surface air discharge: Heterogeneous mass transfer and liquid chemistry pathways.

    Science.gov (United States)

    Liu, D X; Liu, Z C; Chen, C; Yang, A J; Li, D; Rong, M Z; Chen, H L; Kong, M G

    2016-04-01

    Plasma-liquid interaction is a critical area of plasma science and a knowledge bottleneck for many promising applications. In this paper, the interaction between a surface air discharge and its downstream sample of deionized water is studied with a system-level computational model, which has previously reached good agreement with experimental results. Our computational results reveal that the plasma-induced aqueous species are mainly H(+), nitrate, nitrite, H2O2 and O3. In addition, various short-lived aqueous species are also induced, regardless whether they are generated in the gas phase first. The production/loss pathways for aqueous species are quantified for an air gap width ranging from 0.1 to 2 cm, of which heterogeneous mass transfer and liquid chemistry are found to play a dominant role. The short-lived reactive oxygen species (ROS) and reactive nitrogen species (RNS) are strongly coupled in liquid-phase reactions: NO3 is an important precursor for short-lived ROS, and in turn OH, O2(-) and HO2 play a crucial role for the production of short-lived RNS. Also, heterogeneous mass transfer depends strongly on the air gap width, resulting in two distinct scenarios separated by a critical air gap of 0.5 cm. The liquid chemistry is significantly different in these two scenarios.

  4. Aqueous reactive species induced by a surface air discharge: Heterogeneous mass transfer and liquid chemistry pathways

    Science.gov (United States)

    Liu, D. X.; Liu, Z. C.; Chen, C.; Yang, A. J.; Li, D.; Rong, M. Z.; Chen, H. L.; Kong, M. G.

    2016-01-01

    Plasma-liquid interaction is a critical area of plasma science and a knowledge bottleneck for many promising applications. In this paper, the interaction between a surface air discharge and its downstream sample of deionized water is studied with a system-level computational model, which has previously reached good agreement with experimental results. Our computational results reveal that the plasma-induced aqueous species are mainly H+, nitrate, nitrite, H2O2 and O3. In addition, various short-lived aqueous species are also induced, regardless whether they are generated in the gas phase first. The production/loss pathways for aqueous species are quantified for an air gap width ranging from 0.1 to 2 cm, of which heterogeneous mass transfer and liquid chemistry are found to play a dominant role. The short-lived reactive oxygen species (ROS) and reactive nitrogen species (RNS) are strongly coupled in liquid-phase reactions: NO3 is an important precursor for short-lived ROS, and in turn OH, O2− and HO2 play a crucial role for the production of short-lived RNS. Also, heterogeneous mass transfer depends strongly on the air gap width, resulting in two distinct scenarios separated by a critical air gap of 0.5 cm. The liquid chemistry is significantly different in these two scenarios. PMID:27033381

  5. Activators generated by electron transfer for atom transfer radical polymerization of styrene in the presence of mesoporous silica nanoparticles

    Energy Technology Data Exchange (ETDEWEB)

    Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir [School of Chemistry, University College of Science, University of Tehran, PO Box 14155-6455, Tehran (Iran, Islamic Republic of); Roghani-Mamaqani, Hossein [Department of Polymer Engineering, Sahand University of Technology, PO Box 51335-1996, Tabriz (Iran, Islamic Republic of)

    2014-11-15

    Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presence of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric

  6. ATOM TRANSFER RADICAL POLYMERIZATION OF 2,5-BIS[(4-HEXYLOXYPHENYL)OXYCARBONYL]STYRENE

    Institute of Scientific and Technical Information of China (English)

    Yi Yi; Xing-he Fan; Yong-feng Zhao; Xiao-fang Chen; Xin-hua Wan; Qi-feng Zhou

    2005-01-01

    A side-on liquid crystalline monomer, 2,5-bis[(4-hexyloxyphenyl)oxycarbonyl]styrene) (HPCS), was successfully polymerized via atom transfer radical polymerization (ATRP). The polymerization was catalyzed by CuBr/PMDETA in chlorobenzene at 90℃ with (1-bromoethyl)benzene as the initiator. The polymers have narrow MWD. It is the second example of mesogen-jacketed liquid crystalline polymer (MJLCP) prepared by ATRP.

  7. Radical zinc-atom-transfer-based carbozincation of haloalkynes with dialkylzincs

    Directory of Open Access Journals (Sweden)

    Fabrice Chemla

    2013-02-01

    Full Text Available The formation of alkylidenezinc carbenoids by 1,4-addition/carbozincation of dialkylzincs or alkyl iodides based on zinc atom radical transfer, in the presence of dimethylzinc with β-(propargyloxyenoates having pendant iodo- and bromoalkynes, is disclosed. Formation of the carbenoid intermediate is fully stereoselective at −30 °C and arises from a formal anti-selective carbozincation reaction. Upon warming, the zinc carbenoid is stereochemically labile and isomerizes to its more stable form.

  8. Catalytic atom-transfer radical cyclization by copper/bipyridine species encapsulated in polysiloxane gel.

    Science.gov (United States)

    Motoyama, Yukihiro; Kamo, Kazuyuki; Yuasa, Akihiro; Nagashima, Hideo

    2010-04-07

    Novel polysiloxane gel, in which CuCl/bipyridine species are immobilized, is prepared by treatment of polymethylhydrosiloxane with 4,4'-bis[(2-propenyl)oxy]-2,2'-bipyridine and 1,5-hexadine in the presence of Karstedt's catalyst followed by addition of CuCl. This polysiloxane gel acts as a reusable catalyst in the atom-transfer radical cyclization of alpha-halogenated acetamide derivatives in high turnover numbers without allowing leakage of the metal species.

  9. Seawater uranium sorbents: preparation from a mesoporous copolymer initiator by atom-transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Yue, Yanfeng; Mayes, Richard T.; Fulvio, Pasquale F.; Sun, Xiao-Guang [Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Kim, Jungseung; Tsouris, Costas [Energy and Transportation Science Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Chen, Jihua [Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Brown, Suree [Department of Chemistry, University of Tennessee, Knoxville, TN (United States); Dai, Sheng [Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN (United States); Department of Chemistry, University of Tennessee, Knoxville, TN (United States)

    2013-12-09

    Nanoporous template-free initiators for atom-transfer radical polymerization (ATRP) were synthesized with surface and framework initiator sites and tailorable pore structures. Polyacrylonitrile grown on one initiator was converted into polyamidoxime to generate a uranium sorbent for seawater extraction with a high uptake rate and capacity relative to those of nonwoven irradiation-grafted polyethylene-fiber composites. (Copyright copyright 2013 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  10. Local group modes and the dynamics of intramolecular energy transfer across a heavy atom

    OpenAIRE

    Lopez, Vicente; Fairen, Victor; Lederman, Steven M.; Marcus, R.A

    1986-01-01

    The dynamics of energy transfer is discussed for a model system in which two ligands are separated by a heavy atom. Numerical and analytical results are given for the case that each ligand is a CC. In the quasiperiodic regime, the dynamics are interpreted using perturbation theory. Local group modes involved in an intramolecular energy localization which can occur in this regime are identified. An approximate separation of the primarily ligand–ligand motions from the primarily ligand–metal–li...

  11. Bibliography on electron transfer processes in ion-ion/atom/molecule collisions. Updated 1997

    Energy Technology Data Exchange (ETDEWEB)

    Tawara, H.

    1997-04-01

    Following our previous compilations (IPPJ-AM-45 (1986), NIFS-DATA-7 (1990), NIFS-DATA-20 (1993)), bibliographic information on experimental and theoretical studies on electron transfer processes in ion-ion/atom/molecule collisions is up-dated. The references published through 1954-1996 are listed in the order of the publication year. For easy finding of the references for a combination of collision partners, a simple list is provided. (author)

  12. Coherence preservation of a single neutral atom qubit transferred between magic-intensity optical traps

    CERN Document Server

    Yang, Jiaheng; Guo, Ruijun; Xu, Peng; Wang, Kunpeng; Sheng, Cheng; Liu, Min; Wang, Jin; Derevianko, Andrei; Zhan, Mingsheng

    2016-01-01

    We demonstrate that the coherence of a single mobile atomic qubit can be well preserved during a transfer process among different optical dipole traps (ODTs). This is a prerequisite step in realizing a large-scale neutral atom quantum information processing platform. A qubit encoded in the hyperfine manifold of $^{87}$Rb atom is dynamically extracted from the static quantum register by an auxiliary moving ODT and reinserted into the static ODT. Previous experiments were limited by decoherences induced by the differential light shifts of qubit states. Here we apply a magic-intensity trapping technique which mitigates the detrimental effects of light shifts and substantially enhances the coherence time to $225 \\pm 21\\,\\mathrm{ms}$. The experimentally demonstrated magic trapping technique relies on the previously neglected hyperpolarizability contribution to the light shifts, which makes the light shift dependence on the trapping laser intensity to be parabolic. Because of the parabolic dependence, at a certain ...

  13. In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes.

    Science.gov (United States)

    Lee, Juneyoung; Grandner, Jessica M; Engle, Keary M; Houk, K N; Grubbs, Robert H

    2016-06-08

    Ruthenium benzylidene complexes are well-known as olefin metathesis catalysts. Several reports have demonstrated the ability of these catalysts to also facilitate atom transfer radical (ATR) reactions, such as atom transfer radical addition (ATRA) and atom transfer radical polymerization (ATRP). However, while the mechanism of olefin metathesis with ruthenium benzylidenes has been well-studied, the mechanism by which ruthenium benzylidenes promote ATR reactions remains unknown. To probe this question, we have analyzed seven different ruthenium benzylidene complexes for ATR reactivity. Kinetic studies by (1)H NMR revealed that ruthenium benzylidene complexes are rapidly converted into new ATRA-active, metathesis-inactive species under typical ATRA conditions. When ruthenium benzylidene complexes were activated prior to substrate addition, the resulting activated species exhibited enhanced kinetic reactivity in ATRA with no significant difference in overall product yield compared to the original complexes. Even at low temperature, where the original intact complexes did not catalyze the reaction, preactivated catalysts successfully reacted. Only the ruthenium benzylidene complexes that could be rapidly transformed into ATRA-active species could successfully catalyze ATRP, whereas other complexes preferred redox-initiated free radical polymerization. Kinetic measurements along with additional mechanistic and computational studies show that a metathesis-inactive ruthenium species, generated in situ from the ruthenium benzylidene complexes, is the active catalyst in ATR reactions. Based on data from (1) H, (13)C, and (31)P NMR spectroscopy and X-ray crystallography, we suspect that this ATRA-active species is a RuxCly(PCy3)z complex.

  14. TRANSFER

    African Journals Online (AJOL)

    Chemistry Department, Kenyatta University, P. 0. Box 43844 ... harvester (X) [L 2] in a manner consistent with the following Forster equation for long range energy transfer [3-7]. .... sensitive foods, chemical reactors and essences. Recently we ...

  15. Hydroperoxyl Radicals (HOO(.) ): Vitamin E Regeneration and H-Bond Effects on the Hydrogen Atom Transfer.

    Science.gov (United States)

    Cedrowski, Jakub; Litwinienko, Grzegorz; Baschieri, Andrea; Amorati, Riccardo

    2016-11-07

    Hydroperoxyl (HOO(.) ) and alkylperoxyl (ROO(.) ) radicals show a different behavior in H-atom-transfer processes. Both radicals react with an analogue of α-tocopherol (TOH), but HOO(.) , unlike ROO(.) , is able to regenerate TOH by a fast H-atom transfer: TO(.) +HOO(.) →TOH+O2 . The kinetic solvent effect on the H-atom transfer from TOH to HOO(.) is much stronger than that observed for ROO(.) because noncovalent interactions with polar solvents (Solv⋅⋅⋅HOO(.) ) destabilize the transition state.

  16. A model for energy transfer in collisions of atoms with highly excited molecules.

    Science.gov (United States)

    Houston, Paul L; Conte, Riccardo; Bowman, Joel M

    2015-05-21

    A model for energy transfer in the collision between an atom and a highly excited target molecule has been developed on the basis of classical mechanics and turning point analysis. The predictions of the model have been tested against the results of trajectory calculations for collisions of five different target molecules with argon or helium under a variety of temperatures, collision energies, and initial rotational levels. The model predicts selected moments of the joint probability distribution, P(Jf,ΔE) with an R(2) ≈ 0.90. The calculation is efficient, in most cases taking less than one CPU-hour. The model provides several insights into the energy transfer process. The joint probability distribution is strongly dependent on rotational energy transfer and conservation laws and less dependent on vibrational energy transfer. There are two mechanisms for rotational excitation, one due to motion normal to the intermolecular potential and one due to motion tangential to it and perpendicular to the line of centers. Energy transfer is found to depend strongly on the intermolecular potential and only weakly on the intramolecular potential. Highly efficient collisions are a natural consequence of the energy transfer and arise due to collisions at "sweet spots" in the space of impact parameter and molecular orientation.

  17. Atoms

    Institute of Scientific and Technical Information of China (English)

    刘洪毓

    2007-01-01

    Atoms(原子)are all around us.They are something like the bricks (砖块)of which everything is made. The size of an atom is very,very small.In just one grain of salt are held millions of atoms. Atoms are very important.The way one object acts depends on what

  18. Fine Control over Site and Substrate Selectivity in Hydrogen Atom Transfer-Based Functionalization of Aliphatic C-H Bonds.

    Science.gov (United States)

    Salamone, Michela; Carboni, Giulia; Bietti, Massimo

    2016-10-07

    The selective functionalization of unactivated aliphatic C-H bonds over intrinsically more reactive ones represents an ongoing challenge of synthetic chemistry. Here we show that in hydrogen atom transfer (HAT) from the aliphatic C-H bonds of alkane, ether, alcohol, amide, and amine substrates to the cumyloxyl radical (CumO(•)) fine control over site and substrate selectivity is achieved by means of acid-base interactions. Protonation of the amines and metal ion binding to amines and amides strongly deactivates the C-H bonds of these substrates toward HAT to CumO(•), providing a powerful method for selective functionalization of unactivated or intrinsically less reactive C-H bonds. With 5-amino-1-pentanol, site-selectivity has been drastically changed through protonation of the strongly activating NH2 group, with HAT that shifts to the C-H bonds that are adjacent to the OH group. In the intermolecular selectivity studies, trifluoroacetic acid, Mg(ClO4)2, and LiClO4 have been employed in a orthogonal fashion for selective functionalization of alkane, ether, alcohol, and amide (or amine) substrates in the presence of an amine (or amide) one. Ca(ClO4)2, that promotes deactivation of amines and amides by Ca(2+) binding, offers, moreover, the opportunity to selectively functionalize the C-H bonds of alkane, ether, and alcohol substrates in the presence of both amines and amides.

  19. Handshake electron transfer from hydrogen Rydberg atoms incident at a series of metallic thin films

    CERN Document Server

    Gibbard, Jemma A

    2016-01-01

    Thin metallic films have a 1D quantum well along the surface normal direction, which yields particle-in-a-box style electronic quantum states. However the quantum well is not infinitely deep and the wavefunctions of these states penetrate outside the surface where the electron is bound by its own image-charge attraction. Therefore a series of discrete, vacant states reach out from the thin film into the vacuum increasing the probability of electron transfer from an external atom or molecule to the thin film, especially for the resonant case where the quantum well energy matches that of the Rydberg atom. We show that `handshake' electron transfer from a highly excited Rydberg atom to these thin-film states is experimentally measurable. Thicker films, have a wider 1D box, changing the energetic distribution and image-state contribution to the thin film wavefunctions, resulting in more resonances. Calculations successfully predict the number of resonances and the nature of the thin-film wavefunctions for a given...

  20. Handshake electron transfer from hydrogen Rydberg atoms incident at a series of metallic thin films.

    Science.gov (United States)

    Gibbard, J A; Softley, T P

    2016-06-21

    Thin metallic films have a 1D quantum well along the surface normal direction, which yields particle-in-a-box style electronic quantum states. However the quantum well is not infinitely deep and the wavefunctions of these states penetrate outside the surface where the electron is bound by its own image-charge attraction. Therefore a series of discrete, vacant states reach out from the thin film into the vacuum increasing the probability of electron transfer from an external atom or molecule to the thin film, especially for the resonant case where the quantum well energy matches that of the atom. We show that "handshake" electron transfer from a highly excited Rydberg atom to these thin-film states is experimentally measurable. Thicker films have a wider 1D box, changing the energetic distribution and image-state contribution to the thin film wavefunctions, resulting in more resonances. Calculations successfully predict the number of resonances and the nature of the thin-film wavefunctions for a given film thickness.

  1. Atomic layer deposition assisted pattern transfer technology for ultra-thin block copolymer films

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Wenhui; Luo, Jun; Meng, Lingkuan; Li, Junjie; Xiang, Jinjuan; Li, Junfeng; Wang, Wenwu; Chen, Dapeng; Ye, Tianchun; Zhao, Chao

    2016-08-31

    As an emerging developing technique for next-generation lithography, directed self-assembly (DSA) of block copolymer (BCP) has attracted numerous attention and has been a potential alternative to supplement the intrinsic limitations of conventional photolithography. In this work, the self-assembling properties of a lamellar diblock copolymer poly(styrene-b-methylmethacrylate) (PS-b-PMMA, 22k-b-22k, L{sub 0} = 25 nm) on Si substrate and an atomic layer deposition (ALD)-assisted pattern transfer technology for the application of DSA beyond 16/14 nm complementary metal oxide semiconductor (CMOS) technology nodes, were investigated. Firstly, two key processing parameters of DSA, i.e. annealing temperatures and durations of BCP films, were optimized to achieve low defect density and high productivity. After phase separation of BCP films, self-assembling patterns of low defect density should be transferred to the substrate. However, due to the nano-scale thickness and the weak resistance of BCP films to dry etching, it is nearly impossible to transfer the BCP patterns directly to the substrate. Therefore, an ALD-based technology was explored in this work, in which deposited Al{sub 2}O{sub 3} selectively reacts with PMMA blocks thus hardening the PMMA patterns. After removing PS blocks by plasma etching, hardened PMMA patterns were left and transferred to underneath SiO{sub 2} hard mask layer. Using this patterned hard mask, nanowire array of 25 nm pitch were realized on Si substrate. From this work, a high-throughput DSA baseline flow and related ALD-assisted pattern transfer technique were developed and proved to have good capability with the mainstream CMOS technology. - Highlights: • Optimization on self-assembly process for high productivity and low defectivity • Enhancement of etching ratio and resistance by atomic layer deposition (ALD) • A hard mask was used for pattern quality improvement and contamination control.

  2. What is the "best" atomic charge model to describe through-space charge-transfer excitations?

    Science.gov (United States)

    Jacquemin, Denis; Le Bahers, Tangui; Adamo, Carlo; Ciofini, Ilaria

    2012-04-28

    We investigate the efficiency of several partial atomic charge models (Mulliken, Hirshfeld, Bader, Natural, Merz-Kollman and ChelpG) for investigating the through-space charge-transfer in push-pull organic compounds with Time-Dependent Density Functional Theory approaches. The results of these models are compared to benchmark values obtained by determining the difference of total densities between the ground and excited states. Both model push-pull oligomers and two classes of "real-life" organic dyes (indoline and diketopyrrolopyrrole) used as sensitisers in solar cell applications have been considered. Though the difference of dipole moments between the ground and excited states is reproduced by most approaches, no atomic charge model is fully satisfactory for reproducing the distance and amount of charge transferred that are provided by the density picture. Overall, the partitioning schemes fitting the electrostatic potential (e.g. Merz-Kollman) stand as the most consistent compromises in the framework of simulating through-space charge-transfer, whereas the other models tend to yield qualitatively inconsistent values.

  3. Rate constants for 1,5- and 1,6-hydrogen atom transfer reactions of mono-, di-, and tri-aryl-substituted donors, models for hydrogen atom transfers in polyunsaturated fatty acid radicals.

    Science.gov (United States)

    DeZutter, Christopher B; Horner, John H; Newcomb, Martin

    2008-03-06

    Rate constants for 1,5- and 1,6-hydrogen atom transfer reactions in models of polyunsaturated fatty acid radicals were measured via laser flash photolysis methods. Photolyses of PTOC (pyridine-2-thioneoxycarbonyl) ester derivatives of carboxylic acids gave primary alkyl radicals that reacted by 1,5-hydrogen transfer from mono-, di-, and tri-aryl-substituted positions or 1,6-hydrogen transfer from di- and tri-aryl-substituted positions to give UV-detectable products. Rate constants for reactions in acetonitrile at room temperature ranged from 1 x 10(4) to 4 x 10(6) s(-1). The activation energies for a matched pair of 1,5- and 1,6-hydrogen atom transfers giving tri-aryl-substituted radicals were approximately equal, as were the primary kinetic isotope effects, but the 1,5-hydrogen atom transfer reaction was 1 order of magnitude faster at room temperature than the 1,6-hydrogen atom transfer reaction due to a less favorable entropy of activation for the 1,6-transfer reaction. Solvent effects on the rate constants for the 1,5-hydrogen atom transfer reaction of the 2-[2-(diphenylmethyl)phenyl]ethyl radical at ambient temperature were as large as a factor of 2 with the reaction increasing in rate in lower polarity solvents. Hybrid density functional theory computations for the 1,5- and 1,6-hydrogen atom transfers of the tri-aryl-substituted donors were in qualitative agreement with the experimental results.

  4. Optimization of transfer of laser-cooled atom cloud to a quadrupole magnetic

    Indian Academy of Sciences (India)

    S P Ram; S K Tiwari; S R Mishra; H S Rawat

    2014-02-01

    We present here our experimental results on transfer of laser-cooled atom cloud to a quadrupole magnetic trap. We show that by choosing appropriately the ratio of potential energy in magnetic trap to kinetic energy of cloud in molasses, we can obtain the maximum phase-space density in the magnetic trap. These results guide us to choose the value of current to be switched in the quadrupole coils used for magnetic trapping for a given temperature of the cloud after molasses. This study is also useful to set the initial phase-space density of the cloud before evaporative cooling.

  5. Nonradiative transfer of excitation in coherent decay from a Gaussian atomic distribution

    Energy Technology Data Exchange (ETDEWEB)

    Friedberg, Richard, E-mail: rfriedberg1@nyc.rr.com [Physics Department, Columbia University, NY (United States)

    2011-09-14

    Coherent decay of a spherically symmetric ensemble of initially resonantly phased two-level atoms is studied in the scalar photon model, in the continuum and Markov approximations. Emphasis is on the Gaussian distribution, where nonradiative transfer of excitation to excited states orthogonal to the initial one is found to be nonzero even in the limit of short wavelength, whether or not the scalar kernel exp(ik{sub 0}R)/ik{sub 0}R is replaced by its real part. Numerical results are compared to known values for the uniform distribution.

  6. Reverse atom transfer radical polymerization of styrene in emulsion initiated by AIBN or V50

    Institute of Scientific and Technical Information of China (English)

    ZHANG Kai; ZHANG Hongwen; LI Hongtu; WANG Jingyuan

    2005-01-01

    Reverse atom transfer radical polymerization of styrene was conducted in emulsion by using Cu(II)/2,2′- bipydine or Cu(II)/phen complexes, AIBN or V50 as the initiator, Brij-98 or OP-10 as the surfactant. The results of GPC showed that both polymerization processes exhibit living characters when using AIBN as the initiator. However, when V50 was used, the monomer conversion was fairly low and the whole polymerization was not controlled well. The measurement of particle size and its distribution told us that the latex particles were mean and stable when using Brij-98 as the surfactant.

  7. Organic thin film transistors with polymer brush gate dielectrics synthesized by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Pinto, J.C.; Whiting, G.L.; Khodabakhsh, S.

    2008-01-01

    , synthesized by atom transfer radical polymerization (ATRP), were used to fabricate low voltage OFETs with both evaporated pentacene and solution deposited poly(3-hexylthiophene). The semiconductor-dielectric interfaces in these systems were studied with a variety of methods including scanning force microscopy......Low operating voltage is an important requirement that must be met for industrial adoption of organic field-effect transistors (OFETs). We report here solution fabricated polymer brush gate insulators with good uniformity, low surface roughness and high capacitance. These ultra thin polymer films...

  8. Resonant electron transfer in slow collisions of protons with Rydberg hydrogen atoms

    Energy Technology Data Exchange (ETDEWEB)

    Janev, R.K.; Joachain, C.J.; Nedeljkovic, N.N.

    1984-05-01

    The resonant charge-transfer reaction of protons on highly excited hydrogen atoms is considered by taking into account both the tunneling (under-barrier) and the over-barrier (classically allowed) electron transitions. It is demonstrated that in a wide range of variation of the reduced ve- locity v = vn, the classical transition mechanism is predominant. Cross-section calculations for principal quantum numbers n between 10 and 50 are presented. The results for 45< or =n< or =50 are compared with the available experimental data and with other theoretical calculations.

  9. Novel Polymers Based on Atom Transfer Radical Polymerization of 2-Methoxyethyl Acrylate

    DEFF Research Database (Denmark)

    Bednarek, Melania; Jankova Atanasova, Katja; Hvilsted, Søren

    2007-01-01

    Atom transfer radical polymerization (ATRP) has been employed in the polymerization of 2-methoxyethyl acrylate (MEA) initiated by ethyl 2-bromoisobutyrate in bulk or in toluene solution at 90– 95 C with the catalytic systems Cu(I)Br/PMDETA or HMTETA. Kinetics investigations revealed that ATRP...... macroinitiators, however, for the latter the controlled conditions were somehow difficult to maintain. The amphiphilic behavior of the diblock copolymers lead to phase separation resulting in two glass transition temperatures as detected by DSC. Contact angle (Y) investigations with water on PMEA, PMMA...

  10. Surface chemistry of the atomic layer deposition of metals and group III oxides

    Science.gov (United States)

    Goldstein, David Nathan

    Atomic Layer Deposition (ALD) is a thin-film growth technique offering precise control of film thickness and the ability to coat high-aspect-ratio features such as trenches and nanopowders. Unlike other film growth techniques, ALD does not require harsh processing conditions and is not limited by line-of-sight deposition. Emerging applications for ALD materials include semiconductor devices, gas sensors, and water-diffusion barriers. The chemistry behind ALD involves understanding how the precursors interact with surfaces to deposit the desired material. All ALD precursors need to be stable on the substrate to ensure self-limiting behavior yet reactive enough to be easily removed with the second reagent. Recent precursor development has provided many volatile organometallic compounds for most of the periodic table. As the number of precursors increases, proper precursor choice becomes crucial. This is because the film properties, growth rates, and growth temperature vary widely between the precursors. Many of the above traits can be predicted with knowledge of the precursor reaction mechanisms. This thesis aims to link surface reaction mechanisms to observed growth and nucleation trends in metal and oxide ALD systems. The first portion of this thesis explores the mechanisms of two ALD oxide systems. First, I examine the mechanism of ALD alumina with ozone. Ozone is used as an oxidant in the semiconductor industry because the deposited Al 2O3 films possess better insulating properties and ozone is easier to purge from a vacuum system. FT-IR analysis reveals a complicated array of surface intermediates such as formate, carbonate, and methoxy groups that form during Al2O3 growth with ozone. Next, a new method to deposit thin films of Ga2O3 is introduced. Gallium oxide is a transparent conducting oxide that needs expensive solid precursors to be deposited by ALD. I show that trimethylgallium is a good high-temperature ALD precursor that deposits films of Ga2O 3 with

  11. A NOVEL PHOTO-INITIATING SYSTEM FOR ATOM TRANSFER RADICAL POLYMERIZATION OF STYRENE

    Institute of Scientific and Technical Information of China (English)

    Shu-hui Qin; Dong-qi Qin; Kun-yuan Qiu

    2001-01-01

    A novel photo-induced initiating system, 2,2-dimethoxy-2-phenylacetophenone (DMPA)/ferric tri(N,N-diethyldithiocarbamate) [Fe(DC)3], was developed and used for the atom transfer radical polymerization (ATRP) of styrene in toluene. The polymerization proceeds with DMPA as photo-initiator, Fe(DC)3 as catalyst and DC as a reversible transfer group, while the halogen and ligands are free. Well-defined PSt was prepared and the polymerization mechanism revealed by end group analysis belongs to a reverse ATRP. Block copolymer was prepared by using thus obtained PSt as macroinitiator and Fe(DC)2 as catalyst under UV light irradiation via a conventional ATRP process.``

  12. Cytocompatible Polymer Grafting from Individual Living Cells by Atom-Transfer Radical Polymerization.

    Science.gov (United States)

    Kim, Ji Yup; Lee, Bong Soo; Choi, Jinsu; Kim, Beom Jin; Choi, Ji Yu; Kang, Sung Min; Yang, Sung Ho; Choi, Insung S

    2016-12-05

    A cytocompatible method of surface-initiated, activator regenerated by electron transfer, atom transfer radical polymerization (SI-ARGET ATRP) is developed for engineering cell surfaces with synthetic polymers. Dopamine-based ATRP initiators are used for both introducing the ATRP initiator onto chemically complex cell surfaces uniformly (by the material-independent coating property of polydopamine) and protecting the cells from radical attack during polymerization (by the radical-scavenging property of polydopamine). Synthetic polymers are grafted onto the surface of individual yeast cells without significant loss of cell viability, and the uniform and dense grafting is confirmed by various characterization methods including agglutination assay and cell-division studies. This work will provide a strategic approach to the generation of living cell-polymer hybrid structures and open the door to their application in multitude of areas, such as sensor technology, catalysis, theranostics, and cell therapy. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Inserção do conceito de economia atômica no programa de uma disciplina de química orgânica experimental Inclusion of atom economy concept in an experimental organic chemistry undergraduate course

    Directory of Open Access Journals (Sweden)

    Leila Maria Oliveira Coelho Merat

    2003-10-01

    Full Text Available In this paper, the atom economy concepts are applied in a series of experiments during an experimental organic chemistry class, to implement "green chemistry" in an undergraduate course.

  14. Divisible Atoms or None at All? Facing the European Contributions to Developments of Chemistry and Physics in China.

    Science.gov (United States)

    Južnič, Stanislav

    2016-12-01

    atoms is discussed as possible new paradigm which could rename the destructible divisible entities of future physics, and with more difficulties also of chemistry. The word atom meaning indivisible not compound entity is basically in contradiction with the characteristics of item it is supposed to describe. The suffix "a" provides a negation in Ancient Greek language. The suffix should be omitted to use tom (τομος) to manage the actual situation of a-toms (=Toms) as compound of elementary particles. In late 19th century after the European Spring of Nations actually two basically different concepts of atoms of chemists and physicists accomplished a kind of symbioses. The suggestion is put forward that while indivisible atoms soon became contradictions in physics, they still retain some value in chemistry which should be taken into account in the attempt to hange the name of atom. The research of human genome as the atom of genetics is similar in broader sense, while there is no basic problem with the nomenclature of genome. The genome manipulations are far less obstructed with Chinese traditions compared to Christian beliefs.

  15. Excitation of heavy hydrogen-like ions by light atoms in relativistic collisions with large momentum transfers

    CERN Document Server

    Najjari, B

    2012-01-01

    We present a theory for excitation of heavy hydrogen-like projectile-ions by light target-atoms in collisions where the momentum transfers to the atom are very large on the atomic scale. It is shown that in this process the electrons and the nucleus of the atom behave as (quasi-) free particles with respect to each other and that their motion is governed by the field of the nucleus of the ion. The effect of this field on the atomic particles can be crucial for the contribution to the excitation of the ion caused by the electrons of the atom. Due to comparatively very large nuclear mass, however, this field can be neglected in the calculation of the contribution to the excitation due to the nucleus of the atom.

  16. Studying plasmonic resonance modes of hierarchical self-assembled meta-atoms based on their transfer matrix

    Science.gov (United States)

    Suryadharma, Radius N. S.; Fruhnert, Martin; Fernandez-Corbaton, Ivan; Rockstuhl, Carsten

    2017-07-01

    Hierarchical self-assembled meta-atoms are made from a larger number of suitably arranged metallic nanoparticles. They constitute the basic building blocks for isotropic metamaterials. The properties of these meta-atoms are usually studied upon illumination with a plane wave and by analyzing the multipolar composition of the scattered field. This, however, does not always provide full information. The coupling between multiple meta-atoms is usually not considered, and a physical understanding for the cause of the response is often incomplete. Here we overcome these limitations by performing a spectral eigenvalue analysis of the transfer matrix of isolated and coupled self-assembled meta-atoms. Emphasis is put on using a transfer-matrix formulation in either a local or a global coordinate frame. We show that for the magnetic resonance, coupling to nearest neighbors is weak, suggesting the possibility to preserve the response of the isolated meta-atom upon tight packaging in a metamaterial.

  17. Determination of Mercury in Milk by Cold Vapor Atomic Fluorescence: A Green Analytical Chemistry Laboratory Experiment

    Science.gov (United States)

    Armenta, Sergio; de la Guardia, Miguel

    2011-01-01

    Green analytical chemistry principles were introduced to undergraduate students in a laboratory experiment focused on determining the mercury concentration in cow and goat milk. In addition to traditional goals, such as accuracy, precision, sensitivity, and limits of detection in method selection and development, attention was paid to the…

  18. Zeolite Chemistry Studied at the Level of Single Particles, Molecules and Atoms

    NARCIS (Netherlands)

    Ristanovic, Z.

    2016-01-01

    Zeolites are microporous aluminosilicates that find a wide-spread application as catalysts in the oil refining and petrochemical industries. Zeolite acidity and related chemistry play a major role in numerous catalytic processes and it is of significant practical interest to understand their

  19. Atomic-Scale Structure and Local Chemistry of CoFeB-MgO Magnetic Tunnel Junctions.

    Science.gov (United States)

    Wang, Zhongchang; Saito, Mitsuhiro; McKenna, Keith P; Fukami, Shunsuke; Sato, Hideo; Ikeda, Shoji; Ohno, Hideo; Ikuhara, Yuichi

    2016-03-09

    Magnetic tunnel junctions (MTJs) constitute a promising building block for future nonvolatile memories and logic circuits. Despite their pivotal role, spatially resolving and chemically identifying each individual stacking layer remains challenging due to spatially localized features that complicate characterizations limiting understanding of the physics of MTJs. Here, we combine advanced electron microscopy, spectroscopy, and first-principles calculations to obtain a direct structural and chemical imaging of the atomically confined layers in a CoFeB-MgO MTJ, and clarify atom diffusion and interface structures in the MTJ following annealing. The combined techniques demonstrate that B diffuses out of CoFeB electrodes into Ta interstitial sites rather than MgO after annealing, and CoFe bonds atomically to MgO grains with an epitaxial orientation relationship by forming Fe(Co)-O bonds, yet without incorporation of CoFe in MgO. These findings afford a comprehensive perspective on structure and chemistry of MTJs, helping to develop high-performance spintronic devices by atomistic design.

  20. Mechanism of Photoinduced Metal-Free Atom Transfer Radical Polymerization: Experimental and Computational Studies.

    Science.gov (United States)

    Pan, Xiangcheng; Fang, Cheng; Fantin, Marco; Malhotra, Nikhil; So, Woong Young; Peteanu, Linda A; Isse, Abdirisak A; Gennaro, Armando; Liu, Peng; Matyjaszewski, Krzysztof

    2016-02-24

    Photoinduced metal-free atom transfer radical polymerization (ATRP) of methyl methacrylate was investigated using several phenothiazine derivatives and other related compounds as photoredox catalysts. The experiments show that all selected catalysts can be involved in the activation step, but not all of them participated efficiently in the deactivation step. The redox properties and the stability of radical cations derived from the catalysts were evaluated by cyclic voltammetry. Laser flash photolysis (LFP) was used to determine the lifetime and activity of photoexcited catalysts. Kinetic analysis of the activation reaction according to dissociative electron-transfer (DET) theory suggests that the activation occurs only with an excited state of catalyst. Density functional theory (DFT) calculations revealed the structures and stabilities of the radical cation intermediates as well as the reaction energy profiles of deactivation pathways with different photoredox catalysts. Both experiments and calculations suggest that the activation process undergoes a DET mechanism, while an associative electron transfer involving a termolecular encounter (the exact reverse of DET pathway) is favored in the deactivation process. This detailed study provides a deeper understanding of the chemical processes of metal-free ATRP that can aid the design of better catalytic systems. Additionally, this work elucidates several important common pathways involved in synthetically useful organic reactions catalyzed by photoredox catalysts.

  1. Atoms and Molecules in Cavities: From Weak to Strong Coupling in QED Chemistry

    CERN Document Server

    Flick, Johannes; Appel, Heiko; Rubio, Angel

    2016-01-01

    In this work, we provide an overview of how well-established concepts in the fields of quantum chemistry and material sciences have to be adapted when the quantum nature of light becomes important in correlated matter-photon problems. Therefore, we analyze model systems in optical cavities, where the matter-photon interaction is considered from the weak- to the strong coupling limit and for individual photon modes as well as for the multi-mode case. We identify fundamental changes in Born-Oppenheimer surfaces, spectroscopic quantities, conical intersections and efficiency for quantum control. We conclude by applying our novel recently developed quantum-electrodynamical density-functional theory to single-photon emission and show how a straightforward approximation accurately describes the correlated electron-photon dynamics. This paves the road to describe matter-photon interactions from first-principles and addresses the emergence of new states of matter in chemistry and material science.

  2. Atoms and molecules in cavities, from weak to strong coupling in quantum-electrodynamics (QED) chemistry.

    Science.gov (United States)

    Flick, Johannes; Ruggenthaler, Michael; Appel, Heiko; Rubio, Angel

    2017-03-21

    In this work, we provide an overview of how well-established concepts in the fields of quantum chemistry and material sciences have to be adapted when the quantum nature of light becomes important in correlated matter-photon problems. We analyze model systems in optical cavities, where the matter-photon interaction is considered from the weak- to the strong-coupling limit and for individual photon modes as well as for the multimode case. We identify fundamental changes in Born-Oppenheimer surfaces, spectroscopic quantities, conical intersections, and efficiency for quantum control. We conclude by applying our recently developed quantum-electrodynamical density-functional theory to spontaneous emission and show how a straightforward approximation accurately describes the correlated electron-photon dynamics. This work paves the way to describe matter-photon interactions from first principles and addresses the emergence of new states of matter in chemistry and material science.

  3. Atomic scale characterization and surface chemistry of metal modified titanate nanotubes and nanowires

    Science.gov (United States)

    Kukovecz, Ákos; Kordás, Krisztián; Kiss, János; Kónya, Zoltán

    2016-10-01

    Titanates are salts of polytitanic acid that can be synthesized as nanostructures in a great variety concerning crystallinity, morphology, size, metal content and surface chemistry. Titanate nanotubes (open-ended hollow cylinders measuring up to 200 nm in length and 15 nm in outer diameter) and nanowires (solid, elongated rectangular blocks with length up to 1500 nm and 30-60 nm diameter) are the most widespread representatives of the titanate nanomaterial family. This review covers the properties and applications of these two materials from the surface science point of view. Dielectric, vibrational, electron and X-ray spectroscopic results are comprehensively discussed first, then surface modification methods including covalent functionalization, ion exchange and metal loading are covered. The versatile surface chemistry of one-dimensional titanates renders them excellent candidates for heterogeneous catalytic, photocatalytic, photovoltaic and energy storage applications, therefore, these fields are also reviewed.

  4. General model of depolarization and transfer of polarization of singly ionized atoms by collisions with hydrogen atoms

    CERN Document Server

    Derouich, Moncef

    2016-01-01

    Simulations of the generation of the atomic polarization is necessary for interpreting the second solar spectrum. For this purpose, it is important to rigorously determine the effects of the isotropic collisions with neutral hydrogen on the atomic polarization of the neutral atoms, ionized atoms and molecules. Our aim is to treat in generality the problem of depolarizing isotropic collisions between singly ionized atoms and neutral hydrogen in its ground state. Using our numerical code, we computed the collisional depolarization rates of the $p$-levels of ions for large number of values of the effective principal quantum number $n^{*}$ and the Uns\\"old energy $E_p$. Then, genetic programming has been utilized to fit the available depolarization rates. As a result, strongly non-linear relationships between the collisional depolarization rates, $n^{*}$ and $E_p$ are obtained, and are shown to reproduce the original data with accuracy clearly better than 10\\%. These relationships allow quick calculations of the ...

  5. Surface-initiated atom transfer radical polymerization of methyl methacrylate from magnetite nanoparticles at ambient temperature.

    Science.gov (United States)

    Raghuraman, G K; Dhamodharan, R

    2006-07-01

    The synthesis of methyl methacrylate (MMA) brush from the surface of magnetite nanoparticles (core-shell structure), from initiator moieties anchored covalently to the nanoparticles, via room temperature atom transfer radical polymerization (ATRP) is described. The surface-initiated polymerization was carried out from a surface-confined initiator containing a 2-bromoisobutyrate moiety with Cu(I)Br/PMDETA catalytic system. The initiator moiety was covalently anchored to the nanoparticles via a two step modification reaction scheme. Controlled polymerization was observed if ethyl-2-bromoisobutyrate (2-EiBrB) was added as a free/sacrificial initiator. A linear increase of molecular weight and a narrow molecular weight distribution of the PMMA formed in solution, provide evidence for a controlled surface-initiated polymerization, leading to surface-attached polymer brushes under mild conditions. The grafted PMMA provides good stability and dispersibility for the nanoparticles in organic solvents.

  6. THERMOSENSITIVITY OF NARROW-DISPERSED POLY(N-N-PROPYLACRYLAMIDE) PREPARED BY ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Hua-yong Hu; Jing Du; Qing-bin Meng; Zhan-yong Li; Xiao-xia Zhu

    2008-01-01

    Controlled polymerization of N-n-propylacrylamide was achieved by atom transfer radical polymerization (ATRP)in a N,N-dimethylformamide-water mixture (50 vol%) at room temperature with methyl 2-chloropropinonate as initiator andCuCl/tris(2-dimethylaminoethyl)amine as the catalytic system in a ratio of 1:1:1. High molecular weight homopolymers (upto 3.7×104) with narrow molecular weight distribution (less than 1.2) were obtained. The living character of thepolymerization was further demonstrated by self-blocking experiment. An inverse molecular weight dependence of the cloudpoint of narrow-dispersed poly(N-n-propylacrylamide) aqueous solution was determined by turbidimetry and differentialscanning calorimetry, especially for the low molecular weight samples.

  7. Modification of Jute Fibers with Polystyrene via Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Plackett, David; Jankova, Katja Atanassova; Egsgaard, Helge

    2005-01-01

    Atom transfer radical polymerization (ATRP) was investigated as a method of covalently bonding polystyrene to jute (Corchorus capsularis) and as a possible approach to fiber composites with enhanced properties. Jute fibers were modified with a brominated initiator and subsequently ATRP modified...... to attach polystyrene and then examined using SEM, DSC, TGA, FTIR, XPS, elemental analysis, and Py-GC-MS. These techniques confirmed that polystyrene had been covalently bound to the fibers and consequently ATRP-modified jute fiber mats were used to prepare hot-pressed polystyrene composites. Composite...... applications, we conclude that further optimization of the ATRP method is required, possibly targeting higher and more uniform loading of polystyrene on the fibers....

  8. Preparation of polystyrene-grafted titanate nanotubes by in situ atom transfer radical polymerization

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    This work successfully prepared nanohybrids by in situ atom transfer radical polymerization (ATRP) of styrene from titanate nanotubes (TNTs). Fourier-transform infrared (FT-IR), pronton nuclear magnetic resonance spectroscopy (1H NMR), and thermal gravimetric analysis (TGA) were used to verify the successful graft of polystyrene (PS) chains from TNTs. Transmission electron microscopy (TEM) dis-played that the obtained PS-g-TNTs nanohybrids had a core-shell structure of TNT core and PS shell. The grafted PS content was well controlled and increased with increasing of the monomer/initiator ratio. Further copolymerization of tert-butyl acrylate (tBA) from the surface of PS-g-TNTs was studied, illus-trating the "living" characteristics of the surface-induced ATRP method used in this work.

  9. A New Initiator Cholesteryl Chloroformate for Cupper-Based Atom Transfer Radical Polymerization of Methyl Methacrylate

    Institute of Scientific and Technical Information of China (English)

    曹健; 楚娟; 张可达

    2004-01-01

    The polymerization of metyl methacrylate (MMA) was studied in detail by use of CuCl/L as a catalyst and cholesteryl chloroformate (CC) as an initiator. It was found that the atom transfer radical polymerization of MMA could proceed when L equals to a multidentate aliphatic amine ligand, N,N,N',N",N"-penta(methyl acrylate)diethylenetriamine (MA5-DETA), and no polymerization was occurred while L=2,2'-bipyridine and 1,10-phenanthroline. The linear proportionality of the molecular weights to the conversions and straight lines observed in ln[M]0/[M] versus time plots indicated that the present polymerization system had the typical controlled polymerization characteristics.

  10. SYNTHESIS OF BLOCK COPOLYMER BY INTEGRATED LIVING ANIONIC POLYMERIZATION-ATOM TRANSFER RADICAL POLYMERIZATION (ATRP)

    Institute of Scientific and Technical Information of China (English)

    Bing Liu; Feng Liu; Ning Luo; Sheng-kang Ying; Qing Liu

    2000-01-01

    Alpha-trichloroacetoxy terminated polystyrene oligomer (PS-CH2CH2OCOCCl3) and poly-(styrene-b-butadiene)oligomer [P(S-b-B)-CH2CH2OCOCCl3)] were synthesized by living anionic polymeri-zation using n-butyllithium as initiator.Then the PS-CH2CH2OCOCCl3 (PS-Cl3) or P(S-b-B)-CH2CH2O-COCCl3 (PSB-Cl3) was used as the macroinitiator in the polymerization of (meth)acrylates in the presence of CuX/bpy. AB diblock and ABC triblock copolymers were prepared by the integrated living anionic polymerization (LAP)-atom transfer radical polymerization (ATRP). The structures of the PSB-Cl3 and the P(S-b-MMA) were identified by FTIR and 1H-NMR spectrum, respectively. A new way to design block copolymers (the combination of LAP and ATRP) was developed.

  11. Modification of jute fibers with polystyrene via atom transfer radical polymerization.

    Science.gov (United States)

    Plackett, David; Jankova, Katja; Egsgaard, Helge; Hvilsted, Søren

    2005-01-01

    Atom transfer radical polymerization (ATRP) was investigated as a method of covalently bonding polystyrene to jute (Corchorus capsularis) and as a possible approach to fiber composites with enhanced properties. Jute fibers were modified with a brominated initiator and subsequently ATRP modified to attach polystyrene and then examined using SEM, DSC, TGA, FTIR, XPS, elemental analysis, and Py-GC-MS. These techniques confirmed that polystyrene had been covalently bound to the fibers and consequently ATRP-modified jute fiber mats were used to prepare hot-pressed polystyrene composites. Composite specimens were tensile tested and fracture surfaces examined using SEM. Although SEM examination suggested different fracture modes between unmodified fiber and ATRP-modified samples, the tensile strength of modified samples was slightly lower on average than that of unmodified samples. For fiber composite applications, we conclude that further optimization of the ATRP method is required, possibly targeting higher and more uniform loading of polystyrene on the fibers.

  12. Robust entanglement between a movable mirror and atomic ensemble and entanglement transfer in coupled optomechanical system

    Science.gov (United States)

    Bai, Cheng-Hua; Wang, Dong-Yang; Wang, Hong-Fu; Zhu, Ai-Dong; Zhang, Shou

    2016-09-01

    We propose a scheme for the creation of robust entanglement between a movable mirror and atomic ensemble at the macroscopic level in coupled optomechanical system. We numerically simulate the degree of entanglement of the bipartite macroscopic entanglement and show that it depends on the coupling strength between the cavities and is robust with respect to the certain environment temperature. Inspiringly and surprisingly, according to the reported relation between the mechanical damping rate and the mechanical frequency of the movable mirror, the numerical simulation result shows that such bipartite macroscopic entanglement persists for environment temperature up to 170 K, which breaks the liquid nitrogen cooling and liquid helium cooling and largely lowers down the experiment cost. We also investigate the entanglement transfer based on this coupled system. The scheme can be used for the realization of quantum memories for continuous variable quantum information processing and quantum-limited displacement measurements.

  13. Electron transfer, ionization, and excitation in atomic collisions. Progress report, June 15, 1989--June 14, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Winter, T.G.; Alston, S.G.

    1992-08-01

    The research being carried out at Penn State by Winter and Alston addresses the fundamental processes of electron transfer, ionization, and excitation in ion-atom (and ion-ion) collisions. The focus is on intermediate- and higher-energy collisions, corresponding to proton energies of about 25 kilo-electron-volts (keV) or larger. At intermediate energies, where the transition probabilities are not small, many states must be coupled in a large calculation, while at higher energies, perturbative approaches may be used. Several studies have been carried out in the current three-year period; most of these treat systems with only one or two electrons, so that fewer approximations need be made and the basic collisional mechanisms can be more clearly described.

  14. [Electron transfer, ionization, and excitation in atomic collisions]. [Pennsylvania State Univ

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

    Fundamental processes of electron transfer, ionization, and excitation in ion-atom and ion-ion collisions are studied. Attention is focussed on one- and two-electron systems and, more recently, quasi-one-electron systems whose electron-target-ion core can be accurately modeled by one-electron potentials. The basic computational approaches can then be taken with few, if any, approximations, and the underlying collisional mechanisms can be more clearly revealed. At intermediate collision energies (e.g., proton energies for p-He[sup +] collisions on the order of 100 kilo-electron volts), many electronic states are strongly coupled during the collision, a coupled-state approach, such as a coupled-Sturmian-pseudostate approach, is appropriate. At higher collision energies (million electron-volt energies) the coupling is weaker with, however, many more states being coupled together, so that high-order perturbation theory is essential.

  15. Thermosensitive Nanocables Prepared by Surface-Initiated Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Wei Qingshan

    2008-01-01

    Full Text Available Abstract Thermosensitive nanocables consisting of Au nanowire cores and poly(N-isopropylacrylamide sheaths (denoted as Au/PNIPAAm were synthesized by surface-initiated atom transfer radical polymerization (SI-ATRP. The formation of PNIPAAm sheath was verified by Fourier transform infrared (FTIR and hydrogen nuclear magnetic resonance (1H NMR spectroscopy. Transmission electron microscope (TEM results confirmed the core/shell structure of nanohybrids. The thickness and density of PNIPAAm sheaths can be adjusted by controlling the amount of cross-linker during the polymerization. Signature temperature response was observed from Au/cross-linked-PNIPAAm nanocables. Such smart nanocables show immense potentials as building blocks for novel thermosensitive nanodevices in future.

  16. Wideband laser locking to an atomic reference with modulation transfer spectroscopy.

    Science.gov (United States)

    Negnevitsky, V; Turner, L D

    2013-02-11

    We demonstrate that conventional modulated spectroscopy apparatus, used for laser frequency stabilization in many atomic physics laboratories, can be enhanced to provide a wideband lock delivering deep suppression of frequency noise across the acoustic range. Using an acousto-optic modulator driven with an agile oscillator, we show that wideband frequency modulation of the pump laser in modulation transfer spectroscopy produces the unique single lock-point spectrum previously demonstrated with electro-optic phase modulation. We achieve a laser lock with 100 kHz feedback bandwidth, limited by our laser control electronics. This bandwidth is sufficient to reduce frequency noise by 30 dB across the acoustic range and narrows the imputed linewidth by a factor of five.

  17. Robust entanglement between a movable mirror and atomic ensemble and entanglement transfer in coupled optomechanical system.

    Science.gov (United States)

    Bai, Cheng-Hua; Wang, Dong-Yang; Wang, Hong-Fu; Zhu, Ai-Dong; Zhang, Shou

    2016-09-14

    We propose a scheme for the creation of robust entanglement between a movable mirror and atomic ensemble at the macroscopic level in coupled optomechanical system. We numerically simulate the degree of entanglement of the bipartite macroscopic entanglement and show that it depends on the coupling strength between the cavities and is robust with respect to the certain environment temperature. Inspiringly and surprisingly, according to the reported relation between the mechanical damping rate and the mechanical frequency of the movable mirror, the numerical simulation result shows that such bipartite macroscopic entanglement persists for environment temperature up to 170 K, which breaks the liquid nitrogen cooling and liquid helium cooling and largely lowers down the experiment cost. We also investigate the entanglement transfer based on this coupled system. The scheme can be used for the realization of quantum memories for continuous variable quantum information processing and quantum-limited displacement measurements.

  18. Synthesis of End Functional Polymers via Atom Transfer Radical Polymerization in Immobilized Catalytic System

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Cross-linked polystyrene with azo-crown ether functional side chain (PSt-1, 10-dicarbonyl-3,6,9-trizaocylcodecane) was prepared under microwave irradiation and the structure was characterized through FT-IR and element analysis. The functionalized cross-linked polystyrene (cross-link degree, 3.5%) combining with immobilized catalyst system (CuBr and ethyl α-bromo-isobutyrate) can catalyze atom transfer radical polymerization of Styrene. Neat polymer products can be obtained then. Complex of La and the polymer end group (EBiB) was synthesized. The third order nonlinear optical property of the polymer-La complex was investigated and the structure was also characterized by FT-IR and XPS.

  19. On Surface-Initiated Atom Transfer Radical Polymerization Using Diazonium Chemistry To Introduce the Initiator Layer

    DEFF Research Database (Denmark)

    Chernyy, Sergey; Lillethorup, Mie; Ceccato, Marcel

    2011-01-01

    of bromine shows a gradual transition from mushroom to brush-type conformation of the surface anchored chains in both polar and nonpolar reaction medium. Interestingly, it is revealed that very thick polymer brushes, on the order of 1 μm, can be obtained at high bromine content of the initiator layer...

  20. Surface Modification of Nanoporous 1,2-Polybutadiene by Atom Transfer Radical Polymerization or Click Chemistry

    DEFF Research Database (Denmark)

    Guo, Fengxiao; Jankova Atanasova, Katja; Schulte, Lars;

    2010-01-01

    ATRP-grafting of hydrophilic polyacrylates and click of MPEG, the originally hydrophobic samples transformed into hydrophilic nanoporous materials. The successful modification was confirmed by infrared spectroscopy, contact angle measurements and measurements of spontaneous water uptake, while...

  1. Excited-state intramolecular proton transfer to carbon atoms: nonadiabatic surface-hopping dynamics simulations.

    Science.gov (United States)

    Xia, Shu-Hua; Xie, Bin-Bin; Fang, Qiu; Cui, Ganglong; Thiel, Walter

    2015-04-21

    Excited-state intramolecular proton transfer (ESIPT) between two highly electronegative atoms, for example, oxygen and nitrogen, has been intensely studied experimentally and computationally, whereas there has been much less theoretical work on ESIPT to other atoms such as carbon. We have employed CASSCF, MS-CASPT2, RI-ADC(2), OM2/MRCI, DFT, and TDDFT methods to study the mechanistic photochemistry of 2-phenylphenol, for which such an ESIPT has been observed experimentally. According to static electronic structure calculations, irradiation of 2-phenylphenol populates the bright S1 state, which has a rather flat potential in the Franck-Condon region (with a shallow enol minimum at the CASSCF level) and may undergo an essentially barrierless ESIPT to the more stable S1 keto species. There are two S1/S0 conical intersections that mediate relaxation to the ground state, one in the enol region and one in the keto region, with the latter one substantially lower in energy. After S1 → S0 internal conversion, the transient keto species can return back to the S0 enol structure via reverse ground-state hydrogen transfer in a facile tautomerization. This mechanistic scenario is verified by OM2/MRCI-based fewest-switches surface-hopping simulations that provide detailed dynamic information. In these trajectories, ESIPT is complete within 118 fs; the corresponding S1 excited-state lifetime is computed to be 373 fs in vacuum. Most of the trajectories decay to the ground state via the S1/S0 conical intersection in the keto region (67%), and the remaining ones via the enol region (33%). The combination of static electronic structure computations and nonadiabatic dynamics simulations is expected to be generally useful for understanding the mechanistic photophysics and photochemistry of molecules with intramolecular hydrogen bonds.

  2. Effect of current and atomized grain size distribution on the solidification of Plasma Transferred Arc coatings

    Directory of Open Access Journals (Sweden)

    Danielle Bond

    2012-10-01

    Full Text Available Plasma Transferred Arc (PTA is the only thermal spray process that results in a metallurgical bond, being frequently described as a hardfacing process. The superior properties of coatings have been related to the fine microstructures obtained, which are finer than those processed under similar heat input with welding techniques using wire feedstock. This observation suggests that the atomized feedstock plays a role on the solidification of coatings. In this study a model for the role of the powders grains in the solidification of PTA coatings is put forward and discussed. An experiment was setup to discuss the model which involved the deposition of an atomized Co-based alloy with different grain size distributions and deposition currents. X ray diffraction showed that there were no phase changes due to the processing parameters. Microstructure analysis by Laser Confocal Microscopy, dilution with the substrate steel and Vickers microhardness were used the characterized coatings and enriched the discussion confirming the role of the powdered feedstock on the solidification of coatings.

  3. Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.

    Science.gov (United States)

    González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson

    2014-08-07

    In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change.

  4. Rapid cellular internalization of multifunctional star polymers prepared by atom transfer radical polymerization.

    Science.gov (United States)

    Cho, Hong Y; Gao, Haifeng; Srinivasan, Abiraman; Hong, Joanna; Bencherif, Sidi A; Siegwart, Daniel J; Paik, Hyun-Jong; Hollinger, Jeffrey O; Matyjaszewski, Krzysztof

    2010-09-13

    Poly(ethylene glycol) (PEG) star polymers containing GRGDS (Gly-Arg-Gly-Asp-Ser) peptide sequences on the star periphery were synthesized by atom transfer radical polymerization (ATRP) of poly(ethylene glycol) methyl ether methacrylate (PEGMA), GRGDS modified poly(ethylene glycol) acrylate (GRGDS-PEG-Acryl), fluorescein o-methacrylate (FMA), and ethylene glycol dimethacrylate (EGDMA) via an "arm-first" method. Star polymers were approximately 20 nm in diameter, as measured by dynamic light scattering and atomic force microscopy. Conjugation of FMA to the stars was confirmed by fluorescence microscopy, and successful attachment of GRGDS segments to the star periphery was confirmed by (1)H NMR spectroscopy. Both fluorescent PEG star polymers with and without peripheral GRGDS peptide segments were cultured with MC3T3-E1.4 cells. These star polymers were biocompatible with ≥ 90% cell viability after 24 h of incubation. Cellular uptake of PEG star polymers in MC3T3-E1.4 cells was observed by confocal microscopy. Rapid uptake of PEG star polymers with GRGDS peptides (∼ 100% of FITC-positive cells in 15 min measured by flow cytometry) was observed, suggesting enhanced delivery potential of these functional star polymers.

  5. Hot hydrogen atoms reactions of interest in molecular evolution and interstellar chemistry

    Science.gov (United States)

    Becker, R. S.; Hong, K.; Hong, J. H.

    1974-01-01

    Hot hydrogen atoms which are photochemically generated initiate reactions among mixtures of methane, ethane, water and ammonia, to produce ethanol, organic amines, organic acids, and amino acids. Both ethanol and ethyl amine can also act as substrates for formation of amino acids. The one carbon substrate methane is sufficient as a carbon source to produce amino acids. Typical quantum yields for formation of amino acids are approximately 0.00002 to 0.00004. In one experiment, 6 protein amino acids were identified and 8 nonprotein amino acids verified utilizing gas chromatography-mass spectroscopy. We propose that hot atoms, especially hydrogen, initiate reactions in the thermodynamic nonequilibrium environment of interstellar space as well as in the atmospheres of planets.

  6. On the chemistry of hydrides of N atoms and O$^+$ ions

    CERN Document Server

    Awad, Zainab; Williams, David A

    2016-01-01

    Previous work by various authors has suggested that the detection by Herschel/HIFI of nitrogen hydrides along the low density lines of sight towards G10.6-0.4 (W31C) cannot be accounted for by gas-phase chemical models. In this paper we investigate the role of surface reactions on dust grains in diffuse regions, and we find that formation of the hydrides by surface reactions on dust grains with efficiency comparable to that for H$_2$ formation reconciles models with observations of nitrogen hydrides. However, similar surface reactions do not contribute significantly to the hydrides of O$^+$ ions detected by Herschel/HIFI present along many sight lines in the Galaxy. The O$^+$ hydrides can be accounted for by conventional gas-phase chemistry either in diffuse clouds of very low density with normal cosmic ray fluxes or in somewhat denser diffuse clouds with high cosmic ray fluxes. Hydride chemistry in dense dark clouds appears to be dominated by gas-phase ion-molecule reactions.

  7. Kinetics of Atom Transfer Radical Polymerization of Methyl Methacrylate Initiated by Cellulose Chloroacetate in BMIMCI

    Institute of Scientific and Technical Information of China (English)

    LIN Chun-xiang; ZHAN Huai-yu; LIU Ming-hua; FU Shi-yu; LUCIA Lucian

    2013-01-01

    The kinetics of atom transfer radical polymerization(ATRP) of methyl methacrylate(MMA) initiated by cellulose based macroinitator,cellulose chloroacetate,performed in ionic liquid(1-N-butyl-3-methylimidazolium chloride,BMIMCl),dimethyl sulfoxide(DMSO) and dimethyl formamide(DMF) were respectively studied in detail.The polymerizations were carried out under homogeneous conditions with CuBr as catalyst and 2,2'-bipyridine(bpy)as ligand.The dependences of the rate of polymerization on solvent,temperature,monomer/initiator ratio and catalyst/ligand ratio were presented.Plots of ln([M]0/[M]t) vs.time and molecular weight vs.conversion showed a linear dependence,indicating a constant number of propagating species throughout the polymerization as well as a negligible contribution of termination or transfer reactions.On the basis of an Arrhenius plot,the apparent energy of activation(△Eaapp) for ATRP of MMA in BMIMC1 was 16.6 kJ/mol which is much lower than that in diphenyl ether.

  8. Tunable self-assembled spin chains of strongly interacting cold atoms for demonstration of reliable quantum state transfer

    DEFF Research Database (Denmark)

    Loft, N. J. S.; Marchukov, O. V.; Petrosyan, D.

    2016-01-01

    We have developed an efficient computational method to treat long, one-dimensional systems of strongly-interacting atoms forming self-assembled spin chains. Such systems can be used to realize many spin chain model Hamiltonians tunable by the external confining potential. As a concrete...... demonstration, we consider quantum state transfer in a Heisenberg spin chain and we show how to determine the confining potential in order to obtain nearly-perfect state transfer....

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

    Science.gov (United States)

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

    2015-01-01

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

  10. Ion-neutral chemistry at ultralow energies: Dynamics of reactive collisions between laser-cooled Ca^+ ions and Rb atoms in an ion-atom hybrid trap

    CERN Document Server

    Hall, Felix H J; Hegi, Gregor; Raoult, Maurice; Aymar, Mireille; Dulieu, Olivier; Willitsch, Stefan

    2013-01-01

    Cold chemical reactions between laser-cooled Ca^+ ions and Rb atoms were studied in an ion-atom hybrid trap. Reaction rate constants were determined in the range of collision energies /k_B = 20 mK-20 K. The lowest energies were achieved in experiments using single localized Ca^+ ions. Product branching ratios were studied using resonant-excitation mass spectrometry. The dynamics of the reactive processes in this system (non-radiative and radiative charge transfer as well as radiative association leading to the formation of CaRb^+ molecular ions) have been analyzed using high-level quantum-chemical calculations of the potential energy curves of CaRb^+ and quantum-scattering calculations for the radiative channels. For the present low-energy scattering experiments, it is shown that the energy dependence of the reaction rate constants is governed by long-range interactions in line with the classical Langevin model, but their magnitude is determined by short-range non-adiabatic and radiative couplings which only ...

  11. 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

  12. A química orgânica na consolidação dos conceitos de átomo e molécula Organic chemistry in the consolidation of the concepts of atom and molecule

    Directory of Open Access Journals (Sweden)

    Tânia de Oliveira Camel

    2009-01-01

    Full Text Available The present work discusses the appearance of the concepts of valence and molecular structure, and describes the appropriation and evolution of the concept of molecule in the period following the publication of Avogadro's Hypothesis. The point of reference is the development of what became known as Organic Chemistry, which encompassed Pharmacy, Physiological Chemistry, Animal and Plant Chemistry, Chemistry of Dyestuffs, Agricultural Chemistry, and the fledgling Organic Synthesis industry in the early 19th century. The theories formulated in these areas and the quest for accurate atomic weights led to those concepts of valence and molecular structure and to a precise differentiation between atom and molecule.

  13. Atomic charge transfer-counter polarization effects determine infrared CH intensities of hydrocarbons: a quantum theory of atoms in molecules model.

    Science.gov (United States)

    Silva, Arnaldo F; Richter, Wagner E; Meneses, Helen G C; Bruns, Roy E

    2014-11-14

    Atomic charge transfer-counter polarization effects determine most of the infrared fundamental CH intensities of simple hydrocarbons, methane, ethylene, ethane, propyne, cyclopropane and allene. The quantum theory of atoms in molecules/charge-charge flux-dipole flux model predicted the values of 30 CH intensities ranging from 0 to 123 km mol(-1) with a root mean square (rms) error of only 4.2 km mol(-1) without including a specific equilibrium atomic charge term. Sums of the contributions from terms involving charge flux and/or dipole flux averaged 20.3 km mol(-1), about ten times larger than the average charge contribution of 2.0 km mol(-1). The only notable exceptions are the CH stretching and bending intensities of acetylene and two of the propyne vibrations for hydrogens bound to sp hybridized carbon atoms. Calculations were carried out at four quantum levels, MP2/6-311++G(3d,3p), MP2/cc-pVTZ, QCISD/6-311++G(3d,3p) and QCISD/cc-pVTZ. The results calculated at the QCISD level are the most accurate among the four with root mean square errors of 4.7 and 5.0 km mol(-1) for the 6-311++G(3d,3p) and cc-pVTZ basis sets. These values are close to the estimated aggregate experimental error of the hydrocarbon intensities, 4.0 km mol(-1). The atomic charge transfer-counter polarization effect is much larger than the charge effect for the results of all four quantum levels. Charge transfer-counter polarization effects are expected to also be important in vibrations of more polar molecules for which equilibrium charge contributions can be large.

  14. An Integrated Professional and Transferable Skills Course for Undergraduate Chemistry Students

    Science.gov (United States)

    Ashraf, S. Salman; Marzouk, Sayed A. M.; Shehadi, Ihsan A.; Murphy, Brian M.

    2011-01-01

    Upon graduation, chemistry majors often find themselves inadequately prepared for the "real world" that awaits them when they join the workplace. Some employers find chemistry graduates lacking written- and oral-communication skills, critical-thinking skills, group-work skills, as well as the ability to efficiently analyze data and retrieve…

  15. 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.

  16. General model of depolarization and transfer of polarization of singly ionized atoms by collisions with hydrogen atoms

    Science.gov (United States)

    Derouich, M.

    2017-02-01

    Simulations of the generation of the atomic polarization is necessary for interpreting the second solar spectrum. For this purpose, it is important to rigorously determine the effects of the isotropic collisions with neutral hydrogen on the atomic polarization of the neutral atoms, ionized atoms and molecules. Our aim is to treat in generality the problem of depolarizing isotropic collisions between singly ionized atoms and neutral hydrogen in its ground state. Using our numerical code, we computed the collisional depolarization rates of the p-levels of ions for large number of values of the effective principal quantum number n* and the Unsöld energy Ep. Then, genetic programming has been utilized to fit the available depolarization rates. As a result, strongly non-linear relationships between the collisional depolarization rates, n* and Ep are obtained, and are shown to reproduce the original data with accuracy clearly better than 10%. These relationships allow quick calculations of the depolarizing collisional rates of any simple ion which is very useful for the solar physics community. In addition, the depolarization rates associated to the complex ions and to the hyperfine levels can be easily derived from our results. In this work we have shown that by using powerful numerical approach and our collisional method, general model giving the depolarization of the ions can be obtained to be exploited for solar applications.

  17. Characterization of Iron-Imido Species Relevant for N-Group Transfer Chemistry.

    Science.gov (United States)

    Iovan, Diana A; Betley, Theodore A

    2016-02-17

    A sterically accessible tert-butyl-substituted dipyrrinato di-iron(II) complex [((tBu)L)FeCl]2 possessing two bridging chloride atoms was synthesized from the previously reported solvento adduct. Upon treatment with aryl azides, the formation of high-spin Fe(III) species was confirmed by (57)Fe Mössbauer spectroscopy. Crystallographic characterization revealed two possible oxidation products: (1) a terminal iron iminyl from aryl azides bearing ortho isopropyl substituents, ((tBu)L)FeCl((•)NC6H3-2,6-(i)Pr2); or (2) a bridging di-iron imido arising from reaction with 3,5-bis(trifluoromethyl)aryl azide, [((tBu)L)FeCl]2(μ-NC6H3-3,5-(CF3)2). Similar to the previously reported ((Ar)L)FeCl((•)NC6H4-4-(t)Bu), the monomeric iron imido is best described as a high-spin Fe(III) antiferromagnetically coupled to an iminyl radical, affording an S = 2 spin state as confirmed by SQUID magnetometry. The di-iron imido possesses an S = 0 ground state, arising from two high-spin Fe(III) centers weakly antiferromagnetically coupled through the bridging imido ligand. The terminal iron iminyl complex undergoes facile decomposition via intra- or intermolecular hydrogen-atom abstraction (HAA) from an imido aryl ortho isopropyl group, or from 1,4-cyclohexadiene, respectively. The bridging di-iron imido is a competent N-group transfer reagent to cyclic internal olefins as well as styrene. Although solid-state magnetometry indicates an antiferromagnetic interaction between the two iron centers (J = -108.7 cm(-1)) in [((tBu)L)FeCl]2(μ-NC6H3-3,5-(CF3)2), we demonstrate that in solution the bridging imido can facilitate HAA as well as dissociate into a terminal iminyl species, which then can promote HAA. In situ monitoring reveals the di-iron bridging imido is a catalytically competent intermediate, one of several iron complexes observed in the amination of C-H bond substrates or styrene aziridination.

  18. Versatile procedure for site-specific grafting of polymer brushes on patchy particles via atom transfer radical polymerization (ATRP)

    NARCIS (Netherlands)

    Van Ravensteijn, Bas G P; Kegel, Willem K.

    2016-01-01

    We report the preparation of chemically anisotropic colloidal dumbbells of which one lobe is functionalized with chemical handles in the form of chlorine groups. The chlorines are easily converted to azides and subsequently to active initiators for Atom Transfer Radical Polymerization (ATRP) by Clic

  19. ANISOTROPY EFFECTS IN SINGLE-ELECTRON TRANSFER BETWEEN LASER-EXCITED ATOMS AND HIGHLY-CHARGED IONS

    NARCIS (Netherlands)

    1995-01-01

    Recent collision experiments are reviewed in which one-electron transfer between laser excited target atoms and (highly charged) keV-ions has been studied. Especially results showing a dependence of the charge exchange on the initial target orbital alignment are discussed. The question to what exten

  20. Single crystal to single crystal transformation and hydrogen-atom transfer upon oxidation of a cerium coordination compound.

    Science.gov (United States)

    Williams, Ursula J; Mahoney, Brian D; Lewis, Andrew J; DeGregorio, Patrick T; Carroll, Patrick J; Schelter, Eric J

    2013-04-15

    Trivalent and tetravalent cerium compounds of the octamethyltetraazaannulene (H2omtaa) ligand have been synthesized. Electrochemical analysis shows a strong thermodynamic preference for the formal cerium(IV) oxidation state. Oxidation of the cerium(III) congener Ce(Homtaa)(omtaa) occurs by hydrogen-atom transfer that includes a single crystal to single crystal transformation upon exposure to an ambient atmosphere.

  1. ANISOTROPY EFFECTS IN SINGLE-ELECTRON TRANSFER BETWEEN LASER-EXCITED ATOMS AND HIGHLY-CHARGED IONS

    NARCIS (Netherlands)

    Recent collision experiments are reviewed in which one-electron transfer between laser excited target atoms and (highly charged) keV-ions has been studied. Especially results showing a dependence of the charge exchange on the initial target orbital alignment are discussed. The question to what

  2. ANISOTROPY EFFECTS IN SINGLE-ELECTRON TRANSFER BETWEEN LASER-EXCITED ATOMS AND HIGHLY-CHARGED IONS

    NARCIS (Netherlands)

    1995-01-01

    Recent collision experiments are reviewed in which one-electron transfer between laser excited target atoms and (highly charged) keV-ions has been studied. Especially results showing a dependence of the charge exchange on the initial target orbital alignment are discussed. The question to what exten

  3. Ion conducting solid polymer electrolytes based on polypentafluorostyrene-b-polyether-b-polypentafluorostyrene prepared by atom transfer radical polymerization

    DEFF Research Database (Denmark)

    Jankova, Katja; Jannasch, P.; Hvilsted, Søren

    2004-01-01

    Novel triblock copolymers based on central poly( ethylene glycol) ( PEG) or poly( ethylene glycol-co-propylene glycol) (PEGPG) blocks with poly( pentafluorostyrene) (PFS) outer blocks were prepared by Atom Transfer Radical Polymerization (ATRP) with polydispersities on the order of 1.2 - 1...

  4. Charge transfer and formation of reduced Ce{sup 3+} upon adsorption of metal atoms at the ceria (110) surface

    Energy Technology Data Exchange (ETDEWEB)

    Nolan, Michael [Tyndall National Institute, University College Cork, Lee Maltings, Prospect Row, Cork (Ireland)

    2012-04-07

    The modification of cerium dioxide with nanoscale metal clusters is intensely researched for catalysis applications, with gold, silver, and copper having been particularly well studied. The interaction of the metal cluster with ceria is driven principally by a localised interaction between a small number of metal atoms (as small as one) and the surface and understanding the fundamentals of the interaction of metal atoms with ceria surfaces is therefore of great interest. Much attention has been focused on the interaction of metals with the (111) surface of ceria, since this is the most stable surface and can be grown as films, which are probed experimentally. However, nanostructures exposing other surfaces such as (110) show high activity for reactions including CO oxidation and require further study; these nanostructures could be modified by deposition of metal atoms or small clusters, but there is no information to date on the atomic level details of metal-ceria interactions involving the (110) surface. This paper presents the results of density functional theory (DFT) corrected for on-site Coulomb interactions (DFT+U) calculations of the adsorption of a number of different metal atoms at an extended ceria (110) surface; the metals are Au, Ag, Cu, Al, Ga, In, La, Ce, V, Cr, and Fe. Upon adsorption all metals are oxidised, transferring electron(s) to the surface, resulting in localised surface distortions. The precise details depend on the identity of the metal atom. Au, Ag, Cu each transfer one electron to the surface, reducing one Ce ion to Ce{sup 3+}, while of the trivalent metals, Al and La are fully oxidised, but Ga and In are only partially oxidised. Ce and the transition metals are also partially oxidised, with the number of reduced Ce ions possible in this surface no more than three per adsorbed metal atom. The predicted oxidation states of the adsorbed metal atoms should be testable in experiments on ceria nanostructures modified with metal atoms.

  5. Surface modification of carbon nanotubes via combination of mussel inspired chemistry and chain transfer free radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Wan, Qing; Tian, Jianwen; Liu, Meiying; Zeng, Guangjian; Huang, Qiang [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wang, Ke; Zhang, Qingsong [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China); Deng, Fengjie, E-mail: fengjiedeng@aliyun.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Zhang, Xiaoyong, E-mail: xiaoyongzhang1980@gmail.com [Department of Chemistry, Nanchang University, 999 Xuefu Avenue, Nanchang, 330031 (China); Wei, Yen, E-mail: weiyen@tsinghua.edu.cn [Department of Chemistry and the Tsinghua Center for Frontier Polymer Research, Tsinghua University, Beijing, 100084 (China)

    2015-08-15

    Graphical abstract: A novel strategy combination of mussel inspired chemistry and chain transfer free radical polymerization has been developed for surface modification of carbon nanotubes with polymers for the first time. - Highlights: • Surface modification of CNTs via mussel inspired chemistry. • Preparation of aminated polymers through free radical polymerization. • Functionalized CNTs with aminated polymers via Michael addition reaction. • Highly dispersed CNTs in organic and aqueous solution. - Abstract: In this work, a novel strategy for surface modification of carbon nanotubes (CNTs) was developed via combination of mussel inspired chemistry and chain transfer free radical polymerization. First, pristine CNTs were functionalized with polydopamine (PDA), which is formed via self-polymerization of dopamine in alkaline conditions. These PDA functionalized CNTs can be further reacted with amino-terminated polymers (named as PDMC), which was synthesized through chain transfer free radical polymerization using cysteamine hydrochloride as chain transfer agent and methacryloxyethyltrimethyl ammonium chloride as the monomer. PDMC perfectly conjugated with CNT-PDA was ascertained by a series of characterization techniques including transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The dispersibility of obtained CNT nanocomposites (named as CNT-PDA-PDMC) was further examined. Results showed that the dispersibility of CNT-PDA-PDMC in aqueous and organic solutions was obviously enhanced. Apart from PDMC, many other amino-terminated polymers can also be used to functionalization of CNTs via similar strategy. Therefore, the method described in this work should be a general strategy for fabrication various polymer nanocomposites.

  6. Transferable aspherical atom model refinement of protein and DNA structures against ultrahigh-resolution X-ray data.

    Science.gov (United States)

    Malinska, Maura; Dauter, Zbigniew

    2016-06-01

    In contrast to the independent-atom model (IAM), in which all atoms are assumed to be spherical and neutral, the transferable aspherical atom model (TAAM) takes into account the deformed valence charge density resulting from chemical bond formation and the presence of lone electron pairs. Both models can be used to refine small and large molecules, e.g. proteins and nucleic acids, against ultrahigh-resolution X-ray diffraction data. The University at Buffalo theoretical databank of aspherical pseudo-atoms has been used in the refinement of an oligopeptide, of Z-DNA hexamer and dodecamer duplexes, and of bovine trypsin. The application of the TAAM to these data improves the quality of the electron-density maps and the visibility of H atoms. It also lowers the conventional R factors and improves the atomic displacement parameters and the results of the Hirshfeld rigid-bond test. An additional advantage is that the transferred charge density allows the estimation of Coulombic interaction energy and electrostatic potential.

  7. Precision atomic mass spectrometry with applications to fundamental constants, neutrino physics, and physical chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Mount, Brianna J. [Florida State University, Department of Physics (United States); Redshaw, Matthew [National Superconducting Cyclotron Laboratory (United States); Myers, Edmund G., E-mail: myers@nucmar.physics.fsu.edu [Florida State University, Department of Physics (United States)

    2011-07-15

    We present a summary of precision atomic mass measurements of stable isotopes carried out at Florida State University. These include the alkalis {sup 6}Li, {sup 23}Na, {sup 39,41}K, {sup 85,87}Rb, {sup 133}Cs; the rare gas isotopes {sup 84,86}Kr and {sup 129,130,132,136}Xe; {sup 17,18}O, {sup 19}F, {sup 28}Si, {sup 31}P, {sup 32}S; and various isotope pairs of importance to neutrino physics, namely {sup 74,76}Se/{sup 74,76}Ge, {sup 130}Xe/{sup 130}Te, and {sup 115}In/{sup 115}Sn. We also summarize our Penning trap measurements of the dipole moments of PH{sup + } and HCO{sup + }.

  8. Charge-transfer energy in closed-shell ion-atom interactions. [for H and Li ions in He

    Science.gov (United States)

    Alvarez-Rizzatti, M.; Mason, E. A.

    1975-01-01

    The importance of charge-transfer energy in the interactions between closed-shell ions and atoms is investigated. Ab initio calculations on H(plus)-He and Li(plus)-He are used as a guide for the construction of approximate methods for the estimation of the charge-transfer energy for more complicated systems. For many alkali ion-rate gas systems the charge-transfer energy is comparable to the induction energy in the region of the potential minimum, although for doubly charged alkaline-earth ions in rare gases the induction energy always dominates. Surprisingly, an empirical combination of repulsion energy plus asymptotic induction energy plus asymptotic dispersion energy seems to give a fair representation of the total interaction, especially if the repulsion energy is parameterized, despite the omission of any explicit charge-transfer contribution. More refined interaction models should consider the charge-transfer energy contribution.

  9. The transfer of tin and germanium atoms from N-heterocyclic stannylenes and germylenes to diazadienes.

    Science.gov (United States)

    Gans-Eichler, Timo; Gudat, Dietrich; Nättinen, Kalle; Nieger, Martin

    2006-01-23

    New N-heterocyclic stannylenes and germylenes were synthesized by transamination of E[N(SiMe3)2] (E = Ge, Sn) with alpha-amino-aldimines or ethylidene-1,2-diamines and were characterized by spectroscopic methods and in the case of the germylene 10 g by X-ray diffraction. The reactions of several germylenes and stannylenes with diazadienes were studied by using dynamic NMR and computational methods. Experimental and theoretical studies confirmed that metathesis with exchange of the Group 14 atom is feasible for both stannylenes and germylenes, with exchange rates being generally higher for stannylenes. The metathesis of the diazadiene 3 b and the stannylene 1 b follows second-order kinetics and exhibits a sizeable negative entropy of activation. The transfer reaction is inhibited by bulky substituents in both reactants and surprisingly coincides with a suppression of the fragmentation of the stannylene into tin and diazadiene. A connection between oxidative addition and ring fragmentation was also observed in the reaction of 1 f with sulfur. Density functional theory (DFT) calculations suggest that all metathesis reactions proceed via transient spirocyclic [1+4] cycloaddition products, the formation of which is generally endothermic and endergonic. The spirostannanes display a distorted Psi-tbp geometry at the tin atom and their cycloreversion requires low or nearly negligible activation energies; spirogermanes exhibit distorted tetrahedral central atoms and sizeable energy barriers with respect to the same reaction. Complementary studies of cycloadditions of diazadienes to triplet germylenes or stannylenes indicate that these reactions are exothermic. The lowest triplet state in the carbene homologues results from promotion of an electron from an n(N) orbital with pi character rather than the n(C)-sigma orbital as in carbenes, and singlet-triplet excitation energies decrease from carbon to tin. Spirostannanes exhibit a triplet ground-state multiplicity that implies

  10. Resonant charge transfer of hydrogen Rydberg atoms incident at a Cu(100) projected band-gap surface

    CERN Document Server

    Gibbard, J A; Kohlhoff, M; Rennick, C J; So, E; Ford, M; Softley, T P

    2015-01-01

    The charge transfer (ionization) of hydrogen Rydberg atoms (principal quantum number $n=25-34$) incident at a Cu(100) surface is investigated. Unlike fully metallic surfaces, where the Rydberg electron energy is degenerate with the conduction band of the metal, the Cu(100) surface has a projected bandgap at these energies, and only discrete image states are available through which charge transfer can take place. Resonant enhancement of charge transfer is observed at hydrogen principal quantum numbers for which the Rydberg energy matches the energy of one of the image states. The integrated surface ionization signals show clear periodicity as the energies of states with increasing $n$ come in and out of resonance with the image states. The velocity dependence of the surface ionization dynamics is also investigated. Decreased velocity of the incident H atom leads to a greater mean distance of ionization and a lower field required to extract the ion. The surface-ionization profiles (signal versus applied field) ...

  11. Comparison of hydrolytic and non-hydrolytic atomic layer deposition chemistries: Interfacial electronic properties at alumina-silicon interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Marstell, Roderick J.; Strandwitz, Nicholas C., E-mail: strand@lehigh.edu [Department of Materials Science and Engineering and Center for Advanced Materials and Nanotechnology, Lehigh University, Bethlehem, Pennsylvania 18015 (United States)

    2015-11-14

    We report the differences in the passivation and electronic properties of aluminum oxide (Al{sub 2}O{sub 3}) deposited on silicon via traditional hydrolytic atomic layer deposition (ALD) and non-hydrolytic (NH) ALD chemistries. Traditional films were grown using trimethylaluminum (TMA) and water and NHALD films grown using TMA and isopropanol at 300 °C. Hydrolytically grown ALD films contain a smaller amount of fixed charge than NHALD films (oxide fixed charge Q{sub f} {sub Traditional} = −8.1 × 10{sup 11 }cm{sup −2} and Q{sub f} {sub NHALD} = −3.6 × 10{sup 12 }cm{sup −2}), and a larger degree of chemical passivation than NHALD films (density of interface trap states, D{sub it} {sub Traditional} = 5.4 × 10{sup 11 }eV{sup −1 }cm{sup −2} and D{sub it} {sub NHALD} = 2.9 × 10{sup 12 }eV{sup −1 }cm{sup −2}). Oxides grown with both chemistries were found to have a band gap of 7.1 eV. The conduction band offset was 3.21 eV for traditionally grown films and 3.38 eV for NHALD. The increased D{sub it} for NHALD films may stem from carbon impurities in the oxide layer that are at and near the silicon surface, as evidenced by both the larger trap state time constant (τ{sub Traditional} = 2.2 × 10{sup −9} s and τ{sub NHALD} = 1.7 × 10{sup −7} s) and the larger carbon concentration. We have shown that the use of alcohol-based oxygen sources in NHALD chemistry can significantly affect the resulting interfacial electronic behavior presenting an additional parameter for understanding and controlling interfacial electronic properties at semiconductor-dielectric interfaces.

  12. Removal of cefalexin using yeast surface-imprinted polymer prepared by atom transfer radical polymerization.

    Science.gov (United States)

    Li, Xiuxiu; Pan, Jianming; Dai, Jiangdong; Dai, Xiaohui; Ou, Hongxiang; Xu, Longcheng; Li, Chunxiang; Zhang, Rongxian

    2012-10-01

    The first use of yeast as a support in the molecular imprinting field combined with atom transfer radical polymerization was described. Then, the as-prepared molecularly imprinted polymers were characterized by Fourier transmission infrared spectrometry, scanning electron microscope, thermogravimetric analysis, and elemental analysis. The obtained imprinted polymers demonstrated elliptical-shaped particles with the thickness of imprinting layer of 0.63 μm. The batch mode experiments were adopted to investigate the adsorption equilibrium, kinetics, and selectivity. The kinetic properties of imprinted polymers were well described by the pseudo-second-order kinetic equation, indicating the chemical process was the rate-limiting step for the adsorption of cefalexin (CFX). The equilibrium data were well fitted by the Freundlich isotherm, and the multimolecular layers adsorption capacity of imprinted polymers was 34.07 mg g(-1) at 298 K. The selectivity analysis suggested that the imprinted polymers exhibited excellent selective recognition for CFX in the presence of other compounds with related structure. Finally, the analytical method based on the imprinted polymers extraction coupled with high-performance liquid chromatograph was successfully used for CFX analysis in spiked pork and water samples.

  13. Customized atomic force microscopy probe by focused-ion-beam-assisted tip transfer

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Andrew; Butte, Manish J., E-mail: manish.butte@stanford.edu [Department of Pediatrics, Division of Immunology, Allergy and Rheumatology, Stanford University, Stanford, California 94305 (United States)

    2014-08-04

    We present a technique for transferring separately fabricated tips onto tipless atomic force microscopy (AFM) cantilevers, performed using focused ion beam-assisted nanomanipulation. This method addresses the need in scanning probe microscopy for certain tip geometries that cannot be achieved by conventional lithography. For example, in probing complex layered materials or tall biological cells using AFM, a tall tip with a high-aspect-ratio is required to avoid artifacts caused by collisions of the tip's sides with the material being probed. We show experimentally that tall (18 μm) cantilever tips fabricated by this approach reduce squeeze-film damping, which fits predictions from hydrodynamic theory, and results in an increased quality factor (Q) of the fundamental flexural mode. We demonstrate that a customized tip's well-defined geometry, tall tip height, and aspect ratio enable improved measurement of elastic moduli by allowing access to low-laying portions of tall cells (T lymphocytes). This technique can be generally used to attach tips to any micromechanical device when conventional lithography of tips cannot be accomplished.

  14. Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Neti, Venkata S.; Das, Sadananda; Brown, Suree; Janke, Christopher J.; Kuo, Li-Jung; Gill, Gary A.; Dai, Sheng; Mayes, Richard T.

    2017-08-29

    Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g- U/kg of adsorbent) in laboratory screening tests using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. The modest capacity in 21- days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).

  15. Functionalization of nylon membranes via surface-initiated atom-transfer radical polymerization.

    Science.gov (United States)

    Xu, F J; Zhao, J P; Kang, E T; Neoh, K G; Li, J

    2007-07-31

    The ability to manipulate and control the surface properties of nylons is of crucial importance to their widespread applications. In this work, surface-initiated atom-transfer radical polymerization (ATRP) is employed to tailor the functionality of the nylon membrane and pore surfaces in a well-controlled manner. A simple two-step method, involving the activation of surface amide groups with formaldehyde and the reaction of the resulting N-methylol polyamide with 2-bromoisobutyryl bromide, was first developed for the covalent immobilization of ATRP initiators on the nylon membrane and its pore surfaces. Functional polymer brushes of 2-hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol)monomethacrylate (PEGMA) were prepared via surface-initiated ATRP from the nylon membranes. A kinetics study revealed that the chain growth from the membranes was consistent with a "controlled" process. The dormant chain ends of the grafted HEMA polymer (P(HEMA)) and PEGMA polymer (P(PEGMA)) on the nylon membranes could be reactivated for the consecutive surface-initiated ATRP to produce the corresponding nylon membranes functionalized by P(HEMA)-b-P(PEGMA) and P(PEGMA)-b-P(HEMA) diblock copolymer brushes. In addition, membranes with grafted P(HEMA) and P(PEGMA) brushes exhibited good resistance to protein adsorption and fouling under continuous-flow conditions.

  16. HYDROPHILIC MODIFICATION OF PPESK POROUS MEMBRANES VIA AQUEOUS SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Zhuan Yi; You-yi Xu; Li-ping Zhu; Han-bang Dong; Bao-ku Zhu

    2009-01-01

    Hydrophilic surface modification of poly(phthalazinone ether sulfone ketone)(PPESK)porous membranes was achieved via surface-initiated atom transfer radical polymerization(ATRP)in aqueous medium.Prior to ATRP,chloromethyl groups were introduced onto PPESK main chains by chloromethylation.Chloromethylated PPESK(CMPPESK)was fabricated into porous membrane through phase inversion technique.Hydrophilic poly(poly(ethylene glycol)methyl ether methacrylate)(P(PEGMA))brushes were grafted from CMPPESK membrane under the initiation of benzyl chloride groups on membrane surface.The results of Fourier transform infrared(FT-IR)spectroscopy and X-ray photoelectron spectroscopy (XPS)confirmed the grafting of P(PEGMA)chains.Water contact angle measurements and protein adsorption experiments suggested that the hydrophilicity and anti-fouling ability of PPESK membrane were remarkably improved after the grafting of P(PEGMA)brushes.The addition of small amount of water in the reaction solvent apparently accelerated the progress of the grafting reaction.The use of CuCl2 in the catalyst system promoted the controllability of the ATRP reaction.

  17. Colorful Polyelectrolytes: An Atom Transfer Radical Polymerization Route to Fluorescent Polystyrene Sulfonate.

    Science.gov (United States)

    Huberty, Wayne; Tong, Xiaowei; Balamurugan, Sreelatha; Deville, Kyle; Russo, Paul S; Zhang, Donghui

    2016-03-01

    A labeled green fluorescent polystyrene sulfonate (LNaPSS) has been synthesized using atom transfer radical polymerization of a styrene sulfonate monomer with a fluorescent co-monomer, fluorescein thiocyanate-vinyl aniline. As a result this 100 % sulfonated polymer contains no hydrophobic patches along the chain backbone besides the fluorescent marker itself. The concentration of the fluorescent monomer was kept low to maintain the characteristic properties of the anionic polyelectrolyte, LNaPSS. ATRP conditions facilitated the production of polymers spanning a range of molecular weights from 35,000 to 175,000 in gram-scale batches with polydispersity indices of 1.01-1.24. Molecular weight increased with the monomer to initiator ratio. Gel permeation chromatography results show a unimodal distribution, and the polymer structure was also confirmed by (1)H NMR and FT-IR spectroscopy. Fluorescence spectroscopy confirmed covalent bonding of fluorescein isothiocyanate to the polymer, indicating that the polymer is suitable as a probe in fluorescence microscopy. To demonstrate this ability, the polymer was used to locate structural features in salt crystals formed during drying, as in the evaporation of sea mist. A second application to probe diffusion studies is also demonstrated.

  18. Controlled synthesis of photochromic polymer brushes by atom transfer radical polymerization.

    Energy Technology Data Exchange (ETDEWEB)

    Piech, Marcin; Bell, Nelson Simmons; Long, Timothy Michael

    2005-06-01

    This work reports on the grafting of methyl methacrylate polymer brushes containing spirobenzopyran pendant groups from flat silica surfaces and colloidal particles utilizing atom transfer radical polymerization (ATRP). The reaction conditions were optimized with respect to the kind of surface bound initiator, the type of halide and ligand used in the catalytic complex, the presence/absence of untethered initiator, and solvent type. This enabled synthesis of coatings up to 80 {+-} 3 nm thick with controlled spirobenzopyran content. While polymerization kinetics indicate the presence of chain termination reactions, the 'living' character of the process is confirmed by controlled formation of block copolymer brushes. UV/vis spectroscopy was used to characterize the UV-induced isomerization of spirobenzopyran to zwitterionic merocyanine and the thermal back-reaction. Spectral and kinetic analyses of this latter bleaching process points to the existence of free and associated merocyanines in the polymeric brush in both tetrahydrofuran and toluene. However, stabilization of merocyanine species by the polymer matrix is considerably greater in toluene with thermal back-reaction rates approaching those determined for solid dry films.

  19. Surface modification of nanodiamond through metal free atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Shi, Kexin; Heng, Chunning; Mao, Liucheng; Wan, Qing; Huang, Hongye; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2016-12-01

    Surface modification of nanodiamond (ND) with poly(2-methacryloyloxyethyl phosphorylcholine) [poly(MPC)] has been achieved by using metal free surface initiated atom transfer radical polymerization (SI-ATRP). The ATRP initiator was first immobilized on the surface of ND through direct esterification reaction between hydroxyl group of ND and 2-bromoisobutyryl bromide. The initiator could be employed to obtain ND-poly(MPC) nanocomposites through SI-ATRP using an organic catalyst. The final functional materials were characterized by 1H nuclear magnetic resonance, transmission electron microscopy, X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy and thermo gravimetric analysis in detailed. All of these characterization results demonstrated that ND-poly(MPC) have been successfully obtained via metal free photo-initiated SI-ATRP. The ND-poly(MPC) nanocomposites shown enhanced dispersibility in various solvents as well as excellent biocompatibility. As compared with traditional ATRP, the metal free ATRP is rather simple and effective. More importantly, this preparation method avoided the negative influence of metal catalysts. Therefore, the method described in this work should be a promising strategy for fabrication of polymeric nanocomposites with great potential for different applications especially in biomedical fields.

  20. Controlled fabrication of theophylline imprinted polymers on multiwalled carbon nanotubes via atom transfer radical polymerization.

    Science.gov (United States)

    Xu, Jianxiong; Gao, Yong; Li, Huaming

    2011-02-01

    Theophylline imprinted polymers were synthesized on the surface of multiwalled carbon nanotubes via atom transfer radical polymerization using brominated multiwalled carbon nanotubes as an initiator. The nanotube-based initiator was prepared by directly reacting acyl chloride-modified multiwalled carbon nanotubes with 2-hydroxylethyl-2'-bromoisobutyrate. The grafting copolymerization of 2-hydroxyethyl-2-methyl-2-propenoate and ethylene glycol dimethacrylate in the presence of template theophylline led to thin molecularly imprinted polymer films coating multiwalled carbon nanotubes. The thickness of molecularly imprinted polymer films prepared in this study was about 5 nm as determined by transmission electron microscopy. Fourier-transform infrared spectroscopy was utilized to follow the introduction of initiator groups as well as polymers on the carbon nanotube surfaces. Thermogravimetric analysis indicated that the molecularly imprinted polymers were successfully grown from the carbon nanotube surfaces, with the final products having a polymer weight percentage of ca. 50 wt%. The adsorption properties, such as adsorption dynamics, special binding and selective recognition capacity, of the as-prepared molecularly imprinted polymer films were evaluated. The results demonstrated that the composite of molecularly imprinted polymers and multiwalled carbon nanotubes not only possessed a rapid dynamics but also exhibited a good selectivity toward theophylline, compared to caffeine.

  1. Formation of hyperbranched polymers in atom transfer radical copolymerization of MMA and DVB

    Institute of Scientific and Technical Information of China (English)

    2010-01-01

    Hyperbranched poly(methyl methacrylate)s (HPMMAs) have been successfully prepared by atom transfer radical copolymerization of MMA and divinylbenzene (DVB).Kinetic study shows complete consumption of the initiator in 0.5 h,and relatively low polymerization rate when DVB content in the feed was high.By analyzing MALDI-TOF spectra of the resulting copolymers,the linear A n B (n=0,1,2,3) oligomers were formed in 0.5 h of polymerization,and then the oligomers reacted each other to form dimers,further reactions produced HPMMA.The SEC and NMR spectroscopies were used to trace the polymerization,and the results demonstrate that small amount of the branching reactions occur in the initial polymerization,and the branched polymers are significantly generated past a certain conversion depending upon the feed ratios.Raising the content of DVB in the monomer mixture can increase the pendent vinyl groups of the linear oligo-inimers,leading to gelation at low MMA conversion.

  2. Constructing Functional Ionic Membrane Surface by Electrochemically Mediated Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Fen Ran

    2016-01-01

    Full Text Available The sodium polyacrylate (PAANa contained polyethersulfone membrane that was fabricated by preparation of PES-NH2 via nonsolvent phase separation method, the introduction of bromine groups as active sites by grafting α-Bromoisobutyryl bromide, and surface-initiated electrochemically atom transfer radical polymerization (SI-eATRP of sodium acrylate (AANa on the surface of PES membrane. The polymerization could be controlled by reaction condition, such as monomer concentration, electric potential, polymerization time, and modifier concentration. The membrane surface was uniform when the monomer concentration was 0.9 mol/L, the electric potential was −0.12 V, the polymerization time was 8 h, and the modifier concentration was 2 wt.%. The membrane showed excellent hydrophilicity and blood compatibility. The water contact angle decreased from 84° to 68° and activated partial thromboplastin increased from 51 s to 84 s after modification of the membranes.

  3. Formation of cysteine sulfenic acid by oxygen atom transfer from nitrite.

    Science.gov (United States)

    Heinecke, Julie; Ford, Peter C

    2010-07-14

    Cysteine sulfenic acid CysS(O)H is shown to be formed for the reaction of cysteine (CysSH) with aqueous nitrite and the water-soluble ferriheme models Fe(III)(TPPS) (TPPS = meso-tetra(4-sulfonatophenyl)porphyrinato) or Fe(III)(TMPS) (TMPS = meso-tetra(sulfonatomesityl)porphyrinato) at pH 5.8 and 7.4. The other product is the respective ferrous nitrosyl complex Fe(II)(Por)(NO) (Por = TPPS or TMPS). Analogous oxygen atom transfers (OAT) were seen when glutathione (GSH) was used as the substrate. The sulfenic acids, CysS(O)H and GS(O)H, are transient species since they react rapidly with excess thiol to give the respective disulfides, so their presence as reactive intermediates was demonstrated by trapping with dimedone and detecting the resulting adduct using LC/MS. Preliminary kinetics studies are consistent with rate-limiting OAT from a ferric nitro complex Fe(III)(Por)(NO(2)(-)) to CysSH, although this reaction is complicated by a competing dead-end equilibrium to form the thiolate complex (Fe(III)(TPPS)(CysS(-)).

  4. The effects of solution chemistry on the sticking efficiencies of viable Enterococcus faecalis: An atomic force microscopy and modeling study

    Science.gov (United States)

    Cail, Tracy L.; Hochella, Michael F.

    2005-06-01

    Atomic force microscopy (AFM) and Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in combination with the interaction force boundary layer (IFBL) model have been used to empirically and theoretically calculate sticking efficiencies (α) of Enterococcus faecalis cells against a silica glass surface. Sticking efficiencies were calculated in solutions of varying pH and ionic strength and related to maximum distances of transport through a hypothetical soil block using colloid filtration theory. AFM measurements show that the repulsive and attractive forces between E. faecalis cells and a glass surface are a function of ionic strength but are less sensitive to changes in solution pH. Zeta (ζ)-potential measurements of the cells and glass surfaces correlate with these trends. Calculated DLVO energy profiles predict much greater sensitivity to changing solution chemistry. Sticking efficiencies derived from AFM measurements range from 9.6 × 10 -17 to 1 in solutions of low ionic strength (IS) and from 2.6 × 10 -33 to 1 at higher IS. Corresponding α values determined from DLVO theory are essentially zero in all tested solutions. Sticking efficiencies calculated in this study are smaller than values determined from column and field studies in similar systems; however, α derived from AFM data and the IFBL model more closely represent field data than do values calculated from DLVO energy values. A comparison with different methods of calculating α suggests that reversible adhesion may be significant in column-scale transport studies.

  5. Hydrogen-atom transfer reactions from ortho-alkoxy-substituted phenols: an experimental approach.

    Science.gov (United States)

    Amorati, Riccardo; Menichetti, Stefano; Mileo, Elisabetta; Pedulli, Gian Franco; Viglianisi, Caterina

    2009-01-01

    The role of intramolecular hydrogen bonding (HB) on the bond-dissociation enthalpy (BDE) of the phenolic O-H and on the kinetics of H-atom transfer to peroxyl radicals (k(inh)) of several 2-alkoxyphenols was experimentally quantified by the EPR equilibration technique and by inhibited autoxidation studies. These compounds can be regarded as useful models for studying the H-atom abstraction from 2-OR phenols, such as many lignans, reduced coenzyme Q and curcumin. The effects of the various substituents on the BDE(O-H) of 2-methoxy, 2-methoxy-4-methyl, 2,4-dimethoxyphenols versus phenol were measured in benzene solution as -1.8; -3.7; -5.4 kcal mol(-1), respectively. In the case of polymethoxyphenols, significant deviations from the BDE(O-H) values predicted by the additive effects of the substituents were found. The logarithms of the k(inh) constants in cumene were inversely related to the BDE(O-H) values, obeying a linear Evans-Polanyi plot with the same slope of other substituted phenols and a y-axis intercept slightly smaller than that of 2,6-dimethyl phenols. In the cases of phenols having the 2-OR substituent included in a five-membered condensed ring (i.e, compounds 9-11), both conformational isomers in which the OH group points toward or away from the oxygen in position 2 were detected by FTIR spectroscopy and the intramolecular HB strength was thus estimated. The contribution to the BDE(O-H) of the ortho-OR substituent in 9, corrected for intramolecular HB formation, was calculated as -5.6 kcal mol(-1). The similar behaviour of cyclic and non-cyclic ortho-alkoxy derivatives clearly showed that the preferred conformation of the OMe group in ortho-methoxyphenoxyl radicals is that in which the methyl group points away from the phenoxyl oxygen, in contrast to the geometries predicted by DFT calculations.

  6. New chemistry for the growth of first-row transition metal films by atomic layer deposition

    Science.gov (United States)

    Klesko, Joseph Peter

    redox non-innocent nature of a series of recently-reported 1,4-di-tert-butyl-1,3-diazabutadienyl complexes. Other metal complexes using the same ligand system are subsequently evaluated for use as ALD precursors. Finally, a novel approach is described for the stoichiometric control of first-row transition metal manganese and cobalt borate films, whereby the film composition is governed by the elements present in a single precursor. Computational techniques such as density functional theory (DFT) using nucleus-independent chemical shift (NICS) are used to determine the electronic structure and predict the relative reducing power of organic coreagents. Potential ALD precursors are analyzed by 1H and 13C NMR, IR, thermogravimetric and differential thermal analyses (TGA/DTA), melting point and solid state decomposition measurements, magnetic susceptibility measurements, preparative sublimation studies, and solution-screening reactions. Deposition parameters are optimized for successful ALD processes. The composition and surface morphology of the resultant films are studied by scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), auger electron spectroscopy (AES), X-ray diffractometry (XRD), time-of-flight elastic recoil detection analysis (TOF-ERDA), ultraviolet-visible spectroscopy (UV-Vis), and four-point probe resistivity measurements.

  7. Transfer of spin squeezing and particle entanglement between atoms and photons in coupled cavities via two-photon exchange

    OpenAIRE

    Hardal, Ali Ümit Cemal; Müstecaplıoğlu, Özgür E.

    2012-01-01

    Transfer of spin squeezing and particle entanglement between atoms and photons in coupled cavities via two-photon exchange Ali Ü. C. Hardal and Özgür E. Müstecaplıoğlu* Department of Physics, Koç University, Sarıyer, Istanbul 34450, Turkey *Corresponding author: Received March 15, 2012; revised May 19, 2012; accepted May 20, 2012; posted May 22, 2012 (Doc. ID 164811); published June 27, 2012 We examine transfer of particle entanglement and spin sque...

  8. Study on actinoids in boundary ion transfer from an aspect of solution chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Kihara, Sorin; Shirai, Makoto; Matsui, Masakazu [Kyoto Univ., Uji (Japan). Inst. for Chemical Research; Yoshida, Zenko; Aoyagi, Hisao; Kitatsuji, Yoshihiro

    1996-01-01

    This study aimed to elucidate the fundamental properties of boundary ion transfer between water (W) and organic solvent (O) and to apply the results to the study on actinoid ions. First, dissolved states of ion in W and O in relation to boundary transfer were investigated and the transfer stimulation effects by an addition of some agents which can induce their complex formation were examined. Then, a theoretical equation which expresses a relationship between ion-pair extraction reaction and {Delta}Gtr was proposed and proved with {Delta}Gtr of single ion obtained by the use of VITIES, which is an apparatus for voltammetric determination of boundary ion transfer developed by the authors. Single ion transfer in W/O was estimated from the voltammogram based on I-{Delta}V curve (I; electric current which corresponds to the amount of ion transfer and {Delta}V; phase boundary voltage). In addition, determination of actinoid ion transfer in W/O boundary was made by VITIES to clarify the ion transfer energy, velocity and transferred molecular species. Thus, developments of a new isolation method and a trial sensor for actinoid ions were undertaken based on these results. (M.N.)

  9. Suppression of angular momentum transfer in cold collisions of transition metal atoms in ground States with nonzero orbital angular momentum.

    Science.gov (United States)

    Hancox, Cindy I; Doret, S Charles; Hummon, Matthew T; Krems, Roman V; Doyle, John M

    2005-01-14

    The Zeeman relaxation rate in cold collisions of Ti(3d(2)4s(2) 3F2) with He is measured. We find that collisional transfer of angular momentum is dramatically suppressed due to the presence of the filled 4s(2) shell. The degree of electronic interaction anisotropy, which is responsible for Zeeman relaxation, is estimated to be about 200 times smaller in the Ti-He complex than in He complexes with typical non-S-state atoms.

  10. Synthesis of Highly Branched Poly(ε-caprolactone) by Self-condensing Atom Transfer Radical Polymerization of Macroinimers

    Institute of Scientific and Technical Information of China (English)

    2006-01-01

    Branched poly(ε-caprolactone) was synthesized by self-condensing atom transfer radical polymerization of macroinimer, α-acryloyoxy-ω-2-bromopropionyloxy poly(ε-caprolactone),which was prepared by enzyme-catalyzed ring-opening polymerization of ε-caprolactone with 2-hydroxylethyl acrylate as initiator and esterification of the ω-hydroxyl group of the obtained poly(ε-caprolactone) by 2-bromopropionyl bromide.

  11. Chemistry of Cu(acac){sub 2} on Ni(110) and Cu(110) surfaces: Implications for atomic layer deposition processes

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-01-15

    The thermal chemistry of copper(II)acetylacetonate, Cu(acac){sub 2}, on Ni(110) and Cu(110) single-crystal surfaces was probed under vacuum by using x-ray photoelectron spectroscopy (XPS) and temperature programmed desorption (TPD). Some data for acetylacetone (Hacac, CH{sub 3}COCH{sub 2}COCH{sub 3}) adsorbed on Ni(110) are also reported as reference. Chemical transformations were identified in several steps covering a temperature range from 150 K to at least 630 K. The desorption of Hacac and a 3-oxobutanal (CH{sub 3}COCH{sub 2}CHO) byproduct was observed first at 150 and 180 K on Ni(110) and at 160 and 185 K on Cu(110), respectively. Partial loss of the acetylacetonate (acac) ligands and a likely change in adsorption geometry are seen next, with the possible production of HCu(acac), which desorbs at 200 and 235 K from the nickel and copper surfaces, respectively. Molecular Cu(acac){sub 2} desorption is observed on both surfaces at approximately 300 K, probably from recombination of Cu(acac) and acac surface species. The remaining copper atoms on the surface lose their remaining acac ligands to the substrate and become reduced directly to metallic copper. At the same time, the organic ligands follow a series of subsequent surface reactions, probably involving several C-C bond-scissions, to produce other fragments, additional Hacac and HCu(acac) in the gas phase in the case of the copper surface, and acetone on nickel. A significant amount of acac must nevertheless survive on the surface to high temperatures, because Hacac peaks are seen in the TPD at about 515 and 590 K and the C 1s XPS split associated with acac is seen up to close to 500 K. In terms of atomic layer deposition processes, this suggests that cycles could be design to run at such temperatures as long as an effective hydrogenation agent is used as the second reactant to remove the surface acac as Hacac. Only a small fraction of carbon is left behind on Ni after heating to 800 K, whereas more carbon

  12. Transferable potentials for phase equilibria-united atom description of five- and six-membered cyclic alkanes and ethers.

    Science.gov (United States)

    Keasler, Samuel J; Charan, Sophia M; Wick, Collin D; Economou, Ioannis G; Siepmann, J Ilja

    2012-09-13

    While the transferable potentials for phase equilibria-united atom (TraPPE-UA) force field has generally been successful at providing parameters that are highly transferable between different molecules, the polarity and polarizability of a given functional group can be significantly perturbed in small cyclic structures, which limits the transferability of parameters obtained for linear molecules. This has motivated us to develop a version of the TraPPE-UA force field specifically for five- and six-membered cyclic alkanes and ethers. The Lennard-Jones parameters for the methylene group obtained from cyclic alkanes are transferred to the ethers for each ring size, and those for the oxygen atom are common to all compounds for a given ring size. However, the partial charges are molecule specific and parametrized using liquid-phase dielectric constants. This model yields accurate saturated liquid densities and vapor pressures, critical temperatures and densities, normal boiling points, heat capacities, and isothermal compressibilities for the following molecules: cyclopentane, tetrahydrofuran, 1,3-dioxolane, cyclohexane, oxane, 1,4-dioxane, 1,3-dioxane, and 1,3,5-trioxane. The azeotropic behavior and separation factor for the binary mixtures of 1,3-dioxolane/cyclohexane and ethanol/1,4-dioxane are qualitively reproduced.

  13. Room temperature deintercalation of alkali metal atoms from epitaxial graphene by formation of charge-transfer complexes

    Energy Technology Data Exchange (ETDEWEB)

    Shin, H.-C.; Ahn, S. J.; Kim, H. W.; Moon, Y.; Rai, K. B. [Department of Physics, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); Woo, S. H. [College of Pharmacy, Chungnam National University, Daejeon 305–764 (Korea, Republic of); Ahn, J. R., E-mail: jrahn@skku.edu [Department of Physics, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of); SAINT, Sungkyunkwan University, Suwon 440-746 (Korea, Republic of)

    2016-08-22

    Atom (or molecule) intercalations and deintercalations have been used to control the electronic properties of graphene. In general, finite energies above room temperature (RT) thermal energy are required for the intercalations and deintercalations. Here, we demonstrate that alkali metal atoms can be deintercalated from epitaxial graphene on a SiC substrate at RT, resulting in the reduction in density of states at the Fermi level. The change in density of states at the Fermi level at RT can be applied to a highly sensitive graphene sensor operating at RT. Na atoms, which were intercalated at a temperature of 80 °C, were deintercalated at a high temperature above 1000 °C when only a thermal treatment was used. In contrast to the thermal treatment, the intercalated Na atoms were deintercalated at RT when tetrafluorotetracyanoquinodimethane (F4-TCNQ) molecules were adsorbed on the surface. The RT deintercalation occurred via the formation of charge-transfer complexes between Na atoms and F4-TCNQ molecules.

  14. Photoinduced Charge Transfer at Metal Oxide/Oxide Interfaces Prepared with Plasma Enhanced Atomic Layer Deposition

    Science.gov (United States)

    Kaur, Manpuneet

    LiNbO3 and ZnO have shown great potential for photochemical surface reactions and specific photocatalytic processes. However, the efficiency of LiNbO3 is limited due to recombination or back reactions and ZnO exhibits a chemical instability in a liquid cell. In this dissertation, both materials were coated with precise thickness of metal oxide layers to passivate the surfaces and to enhance their photocatalytic efficiency. LiNbO 3 was coated with plasma enhanced atomic layer deposited (PEALD) ZnO and Al2O3, and molecular beam deposited TiO2 and VO2. On the other hand, PEALD ZnO and single crystal ZnO were passivated with PEALD SiO2 and Al2O3. Metal oxide/LiNbO3 heterostructures were immersed in aqueous AgNO3 solutions and illuminated with ultraviolet (UV) light to form Ag nanoparticle patterns. Alternatively, Al2O3 and SiO2/ZnO heterostructures were immersed in K3PO 4 buffer solutions and studied for photoelectrochemical reactions. A fundamental aspect of the heterostructures is the band alignment and band bending, which was deduced from in situ photoemission measurements. This research has provided insight to three aspects of the heterostructures. First, the band alignment at the interface of metal oxides/LiNbO 3, and Al2O3 or SiO2/ZnO were used to explain the possible charge transfer processes and the direction of carrier flow in the heterostructures. Second, the effect of metal oxide coatings on the LiNbO3 with different internal carrier concentrations was related to the surface photochemical reactions. Third is the surface passivation and degradation mechanism of Al2O 3 and SiO2 on ZnO was established. The heterostructures were characterized after stability tests using atomic force microscopy (AFM), scanning electron microscopy (SEM), and cross-section transmission electron microscopy (TEM). The results indicate that limited thicknesses of ZnO or TiO2 on polarity patterned LiNbO3 (PPLN) enhances the Ag+ photoinduced reduction process. ZnO seems more efficient

  15. Insights into the Tunnel Mechanism of Cholesteryl Ester Transfer Protein through All-atom Molecular Dynamics Simulations.

    Science.gov (United States)

    Lei, Dongsheng; Rames, Matthew; Zhang, Xing; Zhang, Lei; Zhang, Shengli; Ren, Gang

    2016-07-01

    Cholesteryl ester transfer protein (CETP) mediates cholesteryl ester (CE) transfer from the atheroprotective high density lipoprotein (HDL) cholesterol to the atherogenic low density lipoprotein cholesterol. In the past decade, this property has driven the development of CETP inhibitors, which have been evaluated in large scale clinical trials for treating cardiovascular diseases. Despite the pharmacological interest, little is known about the fundamental mechanism of CETP in CE transfer. Recent electron microscopy (EM) experiments have suggested a tunnel mechanism, and molecular dynamics simulations have shown that the flexible N-terminal distal end of CETP penetrates into the HDL surface and takes up a CE molecule through an open pore. However, it is not known whether a CE molecule can completely transfer through an entire CETP molecule. Here, we used all-atom molecular dynamics simulations to evaluate this possibility. The results showed that a hydrophobic tunnel inside CETP is sufficient to allow a CE molecule to completely transfer through the entire CETP within a predicted transfer time and at a rate comparable with those obtained through physiological measurements. Analyses of the detailed interactions revealed several residues that might be critical for CETP function, which may provide important clues for the effective development of CETP inhibitors and treatment of cardiovascular diseases.

  16. Surface modification of carbon nanotubes via combination of mussel inspired chemistry and chain transfer free radical polymerization

    Science.gov (United States)

    Wan, Qing; Tian, Jianwen; Liu, Meiying; Zeng, Guangjian; Huang, Qiang; Wang, Ke; Zhang, Qingsong; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2015-08-01

    In this work, a novel strategy for surface modification of carbon nanotubes (CNTs) was developed via combination of mussel inspired chemistry and chain transfer free radical polymerization. First, pristine CNTs were functionalized with polydopamine (PDA), which is formed via self-polymerization of dopamine in alkaline conditions. These PDA functionalized CNTs can be further reacted with amino-terminated polymers (named as PDMC), which was synthesized through chain transfer free radical polymerization using cysteamine hydrochloride as chain transfer agent and methacryloxyethyltrimethyl ammonium chloride as the monomer. PDMC perfectly conjugated with CNT-PDA was ascertained by a series of characterization techniques including transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), thermal gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The dispersibility of obtained CNT nanocomposites (named as CNT-PDA-PDMC) was further examined. Results showed that the dispersibility of CNT-PDA-PDMC in aqueous and organic solutions was obviously enhanced. Apart from PDMC, many other amino-terminated polymers can also be used to functionalization of CNTs via similar strategy. Therefore, the method described in this work should be a general strategy for fabrication various polymer nanocomposites.

  17. Experimental verification of orbital engineering at the atomic scale: Charge transfer and symmetry breaking in nickelate heterostructures

    Science.gov (United States)

    Phillips, Patrick J.; Rui, Xue; Georgescu, Alexandru B.; Disa, Ankit S.; Longo, Paolo; Okunishi, Eiji; Walker, Fred; Ahn, Charles H.; Ismail-Beigi, Sohrab; Klie, Robert F.

    2017-05-01

    Epitaxial strain, layer confinement, and inversion symmetry breaking have emerged as powerful new approaches to control the electronic and atomic-scale structural properties of complex metal oxides. Trivalent rare-earth (RE) nickelate R E NiO3 heterostructures have been shown to be exemplars since the orbital occupancy, degeneracy, and, consequently, electronic/magnetic properties can be altered as a function of epitaxial strain, layer thickness, and superlattice structure. One recent example is the tricomponent LaTiO3-LaNiO3-LaAlO3 superlattice which exhibits charge transfer and orbital polarization as the result of its interfacial dipole electric field. A crucial step towards control of these parameters for future electronic and magnetic device applications is to develop an understanding of both the magnitude and range of the octahedral network's response towards interfacial strain and electric fields. An approach that provides atomic-scale resolution and sensitivity towards the local octahedral distortions and orbital occupancy is therefore required. Here, we employ atomic-resolution imaging coupled with electron spectroscopies and first-principles theory to examine the role of interfacial charge transfer and symmetry breaking in a tricomponent nickelate superlattice system. We find that nearly complete charge transfer occurs between the LaTiO3 and LaNiO3 layers, resulting in a mixed Ni2 +/Ni3 + valence state. We further demonstrate that this charge transfer is highly localized with a range of about 1 unit cell within the LaNiO3 layers. We also show how Wannier-function-based electron counting provides a simple physical picture of the electron distribution that connects directly with formal valence charges. The results presented here provide important feedback to synthesis efforts aimed at stabilizing new electronic phases that are not accessible by conventional bulk or epitaxial film approaches.

  18. Using computational chemistry to understand proton transfer in Green Fluorescent Protein

    Science.gov (United States)

    Hoskin, Christa; Champion, Paul; Sage, Timothy; Benabbas, Abdelkrim; Demidov, Alexander; Salna, Bridget

    2012-02-01

    Green Fluorescent Protein has been studied experimentally by the scientific community for years yet frustratingly little is known about the underlying proton transfer process that produces the green fluorescence. We are trying to elucidate more about this process using Density Functional Theory to prepare and run various calculations on GFP that we compare with kinetics data, Raman and vibrational coherence spectra. I am building a model of wild type GFP that is realistically sized for our computational power, yet still contains key residues that might affect the proton transport process. I will compare my results to those of the E222D GFP mutant. This comparison will allow us to see any differences in energy and normal modes that give insights regarding the proton transfer process. For example, how does it depend on a variety of factors such as temperature, buffer, pH, mutations, etc.? We also plan to examine if the proton transfer propagates through the three donor-acceptor pairs of the ``proton wire'' consecutively versus the three protons on the wire transferring simultaneously. Finally, we will consider how quantum tunneling may be involved in the proton transfer.

  19. Optical pumping and population transfer of nuclear-spin states of caesium atoms in high magnetic fields

    Institute of Scientific and Technical Information of China (English)

    Luo Jun; Sun Xian-Ping; Zeng Xi-Zhi; Zhan Ming-Sheng

    2007-01-01

    Nuclear-spin states of gaseous-state Cs atoms in the ground state are optically manipulated using a Ti:sapphire laser in a magnetic field of 1.516 T, in which optical coupling of the nuclear-spin states is achieved through hyperfine interactions between electrons and nuclei. The steady-state population distribution in the hyperfine Zeeman sublevels of the ground state is detected by using a tunable diode laser. Furthermore, the state population transfer among the of Cs in the ground state due to stochastic collisions between Cs atoms and buffer-gas molecules, is studied at different of the hyperfine interaction can strongly cause the state population transfer and spin-state interchange among the hyperfine Zeeman sublevels. The calculated results maybe explain the steady-state population in hyperfine Zeeman sublevels in terms of rates of optical-pumping, electron-spin flip, nuclear spin flip, and electron-nuclear spin flip-flop transitions among the hyperfine Zeeman sublevels of the ground state of Cs atoms. This method may be applied to the nuclear-spin-based solid-state quantum computation.

  20. Matter, energy, and heat transfer in a classical ballistic atom pump.

    Science.gov (United States)

    Byrd, Tommy A; Das, Kunal K; Mitchell, Kevin A; Aubin, Seth; Delos, John B

    2014-11-01

    A ballistic atom pump is a system containing two reservoirs of neutral atoms or molecules and a junction connecting them containing a localized time-varying potential. Atoms move through the pump as independent particles. Under certain conditions, these pumps can create net transport of atoms from one reservoir to the other. While such systems are sometimes called "quantum pumps," they are also models of classical chaotic transport, and their quantum behavior cannot be understood without study of the corresponding classical behavior. Here we examine classically such a pump's effect on energy and temperature in the reservoirs, in addition to net particle transport. We show that the changes in particle number, of energy in each reservoir, and of temperature in each reservoir vary in unexpected ways as the incident particle energy is varied.

  1. Surface chemistry effects in finite element modeling of heat transfer in (micron)-fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Havstad, M

    2000-12-07

    Equations for modeling surface chemical kinetics by the interaction of gaseous and surface species are presented. The formulation is embedded in a finite element heat transfer code and an ordinary differential equation package is used to solve the surface system of chemical kinetic equations for each iteration within the heat transfer solver. The method is applied to a flow which includes methane and methanol in a microreactor on a chip. A simpler more conventional method, a plug flow reactor model, is then applied to a similar problem. Initial results for steam reforming of methanol are given.

  2. A review of electron-capture and electron-transfer dissociation tandem mass spectrometry in polymer chemistry.

    Science.gov (United States)

    Hart-Smith, Gene

    2014-01-15

    Mass spectrometry (MS)-based studies of synthetic polymers often characterise detected polymer components using mass data alone. However when mass-based characterisations are ambiguous, tandem MS (MS/MS) offers a means by which additional analytical information may be collected. This review provides a synopsis of two particularly promising methods of dissociating polymer ions during MS/MS: electron-capture and electron-transfer dissociation (ECD and ETD, respectively). The article opens with a summary of the basic characteristics and operating principles of ECD and ETD, and relates these techniques to other methods of dissociating gas-phase ions, such as collision-induced dissociation (CID). Insights into ECD- and ETD-based MS/MS, gained from studies into proteins and peptides, are then discussed in relation to polymer chemistry. Finally, ECD- and ETD-based studies into various classes of polymer are summarised; for each polymer class, ECD- and ETD-derived data are compared to CID-derived data. These discussions identify ECD and ETD as powerful means by which unique and diagnostically useful polymer ion fragmentation data may be generated, and techniques worthy of increased utilisation by the polymer chemistry community.

  3. Transfer of the epoxidation of soybean oil from batch to flow chemistry guided by cost and environmental issues.

    Science.gov (United States)

    Kralisch, Dana; Streckmann, Ina; Ott, Denise; Krtschil, Ulich; Santacesaria, Elio; Di Serio, Martino; Russo, Vincenzo; De Carlo, Lucrezia; Linhart, Walter; Christian, Engelbert; Cortese, Bruno; de Croon, Mart H J M; Hessel, Volker

    2012-02-13

    The simple transfer of established chemical production processes from batch to flow chemistry does not automatically result in more sustainable ones. Detailed process understanding and the motivation to scrutinize known process conditions are necessary factors for success. Although the focus is usually "only" on intensifying transport phenomena to operate under intrinsic kinetics, there is also a large intensification potential in chemistry under harsh conditions and in the specific design of flow processes. Such an understanding and proposed processes are required at an early stage of process design because decisions on the best-suited tools and parameters required to convert green engineering concepts into practice-typically with little chance of substantial changes later-are made during this period. Herein, we present a holistic and interdisciplinary process design approach that combines the concept of novel process windows with process modeling, simulation, and simplified cost and lifecycle assessment for the deliberate development of a cost-competitive and environmentally sustainable alternative to an existing production process for epoxidized soybean oil. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  4. A multi-atom and resonant interaction scheme for quantum state transfer and logical gates between two remote cavities via an optical fibre

    CERN Document Server

    Yin, Z; Yin, Zhang-qi; Li, Fu-li

    2007-01-01

    A system consisting of two single-mode cavities spatially separated and connected by an optical fibre and multi two-level atoms trapped in the cavities is considered. If the atoms resonantly and collectively interact with the local cavity fields but there is no direct interaction between the atoms, we show that an ideal quantum state transfer, and highly reliable quantum swap, entangling and controlled-Z gates can be deterministically realized between the distant cavities. We find that the operation of the state-transfer, and swap, entangling and controlled-Z gates can be greatly speeded up as number of the atoms in the cavities increases. We also notice that the effects of spontaneous emission of atoms and photon leakage out of cavity on the quantum processes can also be greatly diminished in the multi-atom case.

  5. Kinetic Studies of Atom Transfer Radical Polymerisations of Styrene and Chloromethylstyrene with Poly(3-hexyl thiophene Macroinitiator

    Directory of Open Access Journals (Sweden)

    Nattawoot Rattanathamwat

    2015-01-01

    Full Text Available Poly(3-hexyl thiophene-b-poly(styrene-co-chloromethylstyrene copolymers, to be used as a prepolymer for preparing donor-acceptor block copolymers for organic solar cells, have been synthesised by reacting P3HT macroinitiators with styrene and chloromethylstyrene via three types of atom transfer radical polymerisation (ATRP systems, which are (1 a normal ATRP, (2 activators generated by electron transfer (AGET, and (3 a simultaneous reverse and normal initiation (SR&NI. The kinetics of these ATRP systems were studied as a function of monomers to the macroinitiator molar ratio. It was found that all of the three types of ATRP systems led to first order kinetics with respect to monomers. The highest rate constant (k of 3.4 × 10−3 s−1 was obtained from the SR&NI ATRP system. The molecular weights of the product determined by the GPC were lower than were the theoretical values. The result was discussed in light of the chain transfer reaction to the poly(chloromethylstyrene repeating units. Morphology of the synthesized block copolymers, examined by an atomic force microscopy (AFM, were also compared and discussed.

  6. Water-Soluble Iron(IV)-Oxo Complexes Supported by Pentapyridine Ligands: Axial Ligand Effects on Hydrogen Atom and Oxygen Atom Transfer Reactivity.

    Science.gov (United States)

    Chantarojsiri, Teera; Sun, Yujie; Long, Jeffrey R; Chang, Christopher J

    2015-06-15

    We report the photochemical generation and study of a family of water-soluble iron(IV)-oxo complexes supported by pentapyridine PY5Me2-X ligands (PY5Me2 = 2,6-bis(1,1-bis(2-pyridyl)ethyl)pyridine; X = CF3, H, Me, or NMe2), in which the oxidative reactivity of these ferryl species correlates with the electronic properties of the axial pyridine ligand. Synthesis of a systematic series of [Fe(II)(L)(PY5Me2-X)](2+) complexes, where L = CH3CN or H2O, and characterizations by several methods, including X-ray crystallography, cyclic voltammetry, and Mössbauer spectroscopy, show that increasing the electron-donating ability of the axial pyridine ligand tracks with less positive Fe(III)/Fe(II) reduction potentials and quadrupole splitting parameters. The Fe(II) precursors are readily oxidized to their Fe(IV)-oxo counterparts using either chemical outer-sphere oxidants such as CAN (ceric ammonium nitrate) or flash-quench photochemical oxidation with [Ru(bpy)3](2+) as a photosensitizer and K2S2O8 as a quencher. The Fe(IV)-oxo complexes are capable of oxidizing the C-H bonds of alkane (4-ethylbenzenesulfonate) and alcohol (benzyl alcohol) substrates via hydrogen atom transfer (HAT) and an olefin (4-styrenesulfonate) substrate by oxygen atom transfer (OAT). The [Fe(IV)(O)(PY5Me2-X)](2+) derivatives with electron-poor axial ligands show faster rates of HAT and OAT compared to their counterparts supported by electron-rich axial donors, but the magnitudes of these differences are relatively modest.

  7. Atmospheric chemistry of 3-pentanol: kinetics, mechanisms, and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOX.

    Science.gov (United States)

    Hurley, M D; Wallington, T J; Bjarrum, M; Javadi, M S; Nielsen, O J

    2008-09-04

    Smog chamber/FTIR techniques were used to study the atmospheric chemistry of 3-pentanol and determine rate constants of k(Cl+3-pentanol) = (2.03 +/- 0.23) x 10 (-10) and k(OH+3-pentanol) = (1.32 +/- 0.15) x 10 (-11) cm (3) molecule (-1) s (-1) in 700 Torr of N 2/O 2 diluent at 296 +/- 2 K. The primary products of the Cl atom initiated oxidation of 3-pentanol in the absence of NO were (with molar yields) 3-pentanone (26 +/- 2%), propionaldehyde (12 +/- 2%), acetaldehyde (13 +/- 2%) and formaldehyde (2 +/- 1%). The primary products of the Cl atom initiated oxidation of 3-pentanol in the presence of NO were (with molar yields) 3-pentanone (51 +/- 4%), propionaldehyde (39 +/- 2%), acetaldehyde (44 +/- 4%) and formaldehyde (4 +/- 1%). The primary products of the OH radical initiated oxidation of 3-pentanol in the presence of NO were (with molar yields) 3-pentanone (58 +/- 3%), propionaldehyde (28 +/- 2%), and acetaldehyde (37 +/- 2%). In all cases the product yields were independent of oxygen concentration over the partial pressure range 10-700 Torr. The reactions of Cl atoms and OH radicals with 3-pentanol proceed 26 +/- 2 and 58 +/- 3%, respectively, via attack on the 3-position to give an alpha-hydroxyalkyl radical, which reacts with O 2 to give 3-pentanone. The results are discussed with respect to the literature data and atmospheric chemistry of 3-pentanol.

  8. Excited state intramolecular charge transfer reaction of 4-(morpholenyl) benzonitrile in solution: Effects of hetero atom in the donor moiety

    Indian Academy of Sciences (India)

    Tuhin Pradhan; Harun Al Rasid Gazi; Ranjit Biswas

    2010-07-01

    An intramolecular charge transfer (ICT) molecule with an extra hetero atom in its donor moiety has been synthesized in order to investigate how ICT reaction is affected by hetero atom replacement. Photo-physical and photo-dynamical properties of this molecule, 4-(morpholenyl)benzonitrile (M6C), have been studied in 20 different solvents. The correlation between the reaction driving force (- ) and activation barrier ( #) has been explored in order to understand the solvent effects (static and dynamic) on the photo-excited ICT reaction in this molecule. A Kramer’s model analysis of the experimentally observed reaction rate constants indicates a solvent-averaged activation barrier of ∼ 4 in the absence of solvent dynamical control. The reaction in M6C is therefore not a barrier-less reaction but close to the limit where conventional kinetics might break down.

  9. Ultracold magnetically tunable interactions without radiative charge transfer losses between Ca$^+$, Sr$^+$, Ba$^+$, and Yb$^+$ ions and Cr atoms

    CERN Document Server

    Tomza, Michał

    2015-01-01

    The Ca$^+$, Sr$^+$, Ba$^+$, and Yb$^+$ ions immersed in an ultracold gas of the Cr atoms are proposed as experimentally feasible heteronuclear systems in which ion-atom interactions at ultralow temperatures can be controlled with magnetically tunable Feshbach resonances without charge transfer and radiative losses. \\textit{Ab initio} techniques are applied to investigate electronic-ground-state properties of the (CaCr)$^+$, (SrCr)$^+$, (BaCr)$^+$, and (YbCr)$^+$ molecular ions. The potential energy curves, permanent electric dipole moments, and static electric dipole polarizabilities are computed. The spin restricted open-shell coupled cluster method restricted to single, double, and noniterative triple excitations, RCCSD(T), and the multireference configuration interaction method restricted to single and double excitations, MRCISD, are employed. The scalar relativistic effects are included within the small-core energy-consistent pseudopotentials. The leading long-range induction and dispersion interaction co...

  10. Elastic, charge transfer, and related transport cross sections for proton impact of atomic hydrogen for astrophysical and laboratory plasma modeling

    Science.gov (United States)

    Schultz, D. R.; Ovchinnikov, S. Yu; Stancil, P. C.; Zaman, T.

    2016-04-01

    Updating and extending previous work (Krstić and Schultz 1999 J. Phys. B: At. Mol. Opt. Phys. 32 3458 and other references) comprehensive calculations were performed for elastic scattering and charge transfer in proton—atomic hydrogen collisions. The results, obtained for 1301 collision energies in the center-of-mass energy range of 10-4-104 eV, are provided for integral and differential cross sections relevant to transport modeling in astrophysical and other plasma environments, and are made available through a website. Use of the data is demonstrated through a Monte Carlo transport simulation of solar wind proton propagation through atomic hydrogen gas representing a simple model of the solar wind interaction with heliospheric neutrals.

  11. Enhancing the quantum state transfer between two atoms in separate cavities via weak measurement and its reversal

    Science.gov (United States)

    Li, Yan-Ling; Huang, Jinsong; Xu, Zhonghui; Xiao, Xing

    2017-10-01

    Taking the advantage of weak measurement and quantum measurement reversal, we propose a scheme to enhance the fidelity of transferring quantum state from one atom trapped in cavity to another distant one trapped in another cavity which is coupled by an optical fiber. It is turned out that the fidelity can be greatly improved even when the system is under serious dissipation. Moreover, the scheme works in both the strong-coupling and weak-coupling regimes. It is also robust to the ratio of the coupling constant between the atoms and the cavity modes to the coupling constant between the fiber and cavity modes. The underlying mechanism can be attributed to the probabilistic nature of weak measurements.

  12. Atomic force microscopy for the study of specially prepared surfaces including transferred Langmuir-Blodgett layers. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Dr. J. D. Miller

    1999-06-02

    During the past four years a major number of surface science research programs in the Department of Metallurgical Engineering at the University of Utah have involved the use of the Atomic Force Microscope (AFM) and the Langmuir-Blodgett (LB) film balance procured with financial assistance from DOE under grant number DE-FG03-96ER76049. These instruments have been used for research in the areas of nonsulfide flotation chemistry, mineral processing, waste paper deinking, water treatment, treatment of contaminated soil, coal preparation, and plastics recycling. In addition, the AFM and LB film balance have been of great help to university researchers in other departments at the University of Utah and elsewhere, as well as researchers from industry.

  13. Characterization of Iron-Imido Species Relevant for N-Group Transfer Chemistry

    OpenAIRE

    Iovan, Diana A.; Betley, Theodore A.

    2016-01-01

    A sterically accessible tert-butyl-substituted dipyrrinato di-iron(II) complex [(tBuL)FeCl]2 possessing two bridging chloride atoms was synthesized from the previously reported solvento adduct. Upon treatment with aryl azides, the formation of high-spin FeIII species was confirmed by 57Fe Mössbauer spectroscopy. Crystallographic characterization revealed two possible oxidation products: (1) a terminal iron iminyl from aryl azides bearing ortho isopropyl substituents, (tBuL)FeCl(•NC6H3-2,6-iPr...

  14. Surface-Initiated Atom Transfer Radical Polymerization and Electrografting Technique as a Means For Attaining Tailor-Made Polymer Coatings

    DEFF Research Database (Denmark)

    Chernyy, Sergey

    2012-01-01

    Atom transfer radical polymerization initiated from a surface of various substrates (SI-ATRP) has become a progressively popular technique for obtaining thin polymer films with predetermined properties. The present work addresses the main features of SI-ATRP with respect to the controllability......, the kinetics of polymerization was analyzed in-situ and in real time by QCM. For the first time the specific adsorption of monovalent copper to the surface tethered initiator was detected by observation of an activation period preceding the onset of polymerization. The driving force for high affinity of copper...

  15. Determining the Transference Number of H[superscript +](aq) by a Modified Moving Boundary Method: A Directed Study for the Undergraduate Physical Chemistry Laboratory

    Science.gov (United States)

    Dabke, Rajeev B.; Gebeyehu, Zewdu; Padelford, Jonathan

    2012-01-01

    A directed study for the undergraduate physical chemistry laboratory for determining the transference number of H[superscript +](aq) using a modified moving boundary method is presented. The laboratory study combines Faraday's laws of electrolysis with mole ratios and the perfect gas equation. The volume of hydrogen gas produced at the cathode is…

  16. Deposition of O atomic layers on Si(100) substrates for epitaxial Si-O superlattices: investigation of the surface chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Jayachandran, Suseendran, E-mail: suseendran.jayachandran@imec.be [KU Leuven, Department of Metallurgy and Materials, Castle Arenberg 44, B-3001 Leuven (Belgium); IMEC, Kapeldreef 75, 3001 Leuven (Belgium); Delabie, Annelies; Billen, Arne [KU Leuven, Department of Chemistry, Celestijnenlaan 200F, B-3001 Leuven (Belgium); IMEC, Kapeldreef 75, 3001 Leuven (Belgium); Dekkers, Harold; Douhard, Bastien; Conard, Thierry; Meersschaut, Johan; Caymax, Matty [IMEC, Kapeldreef 75, 3001 Leuven (Belgium); Vandervorst, Wilfried [KU Leuven, Department of Physics and Astronomy, Celestijnenlaan 200D, B-3001 Leuven (Belgium); IMEC, Kapeldreef 75, 3001 Leuven (Belgium); Heyns, Marc [KU Leuven, Department of Metallurgy and Materials, Castle Arenberg 44, B-3001 Leuven (Belgium); IMEC, Kapeldreef 75, 3001 Leuven (Belgium)

    2015-01-01

    Highlights: • Atomic layer is deposited by O{sub 3} chemisorption reaction on H-terminated Si(100). • O-content has critical impact on the epitaxial thickness of the above-deposited Si. • Oxygen atoms at dimer/back bond configurations enable epitaxial Si on O atomic layer. • Oxygen atoms at hydroxyl and more back bonds, disable epitaxial Si on O atomic layer. - Abstract: Epitaxial Si-O superlattices consist of alternating periods of crystalline Si layers and atomic layers of oxygen (O) with interesting electronic and optical properties. To understand the fundamentals of Si epitaxy on O atomic layers, we investigate the O surface species that can allow epitaxial Si chemical vapor deposition using silane. The surface reaction of ozone on H-terminated Si(100) is used for the O deposition. The oxygen content is controlled precisely at and near the atomic layer level and has a critical impact on the subsequent Si deposition. There exists only a small window of O-contents, i.e. 0.7–0.9 atomic layers, for which the epitaxial deposition of Si can be realized. At these low O-contents, the O atoms are incorporated in the Si-Si dimers or back bonds (-OSiH), with the surface Si atoms mainly in the 1+ oxidation state, as indicated by infrared spectroscopy. This surface enables epitaxial seeding of Si. For O-contents higher than one atomic layer, the additional O atoms are incorporated in the Si-Si back bonds as well as in the Si-H bonds, where hydroxyl groups (-Si-OH) are created. In this case, the Si deposition thereon becomes completely amorphous.

  17. Tetrapositive plutonium, neptunium, uranium, and thorium coordination complexes: chemistry revealed by electron transfer and collision induced dissociation.

    Science.gov (United States)

    Gong, Yu; Tian, Guoxin; Rao, Linfeng; Gibson, John K

    2014-04-17

    The Pu(4+), Np(4+), and U(4+) ions, which have large electron affinities of ∼34.6, ∼33.6, and ∼32.6 eV, respectively, were stabilized from solution to the gas phase upon coordination by three neutral tetramethyl-3-oxa-glutaramide ligands (TMOGA). Both collision induced dissociation (CID) and electron transfer dissociation (ETD) of Pu(TMOGA)3(4+) reveal the propensity for reduction of Pu(IV) to Pu(III), by loss of TMOGA(+) in CID and by simple electron transfer in ETD. The reduction of Pu(IV) is in distinct contrast to retention of Th(IV) in both CID and ETD of Th(TMOGA)3(4+), where only the C-Oether bond cleavage product was observed. U(TMOGA)3(4+) behaves similarly to Th(TMOGA)3(4+) upon CID and ETD, while the fragmentation patterns of Np(TMOGA)3(4+) lie between those of Pu(TMOGA)3(4+) and U(TMOGA)3(4+). It is notable that the gas-phase fragmentation behaviors of these exceptional tetrapositive complexes parallel fundamental differences in condensed phase chemistry within the actinide series, specifically the tendency for reduction from the IV to III oxidation states.

  18. [Electron transfer, ionization, and excitation in atomic collisions]. Final technical report, June 15, 1986--June 14, 1998

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1998-12-31

    The research on theoretical atomic collisions that was funded at The Pennsylvania State University`s Wilkes-Barre Campus by DOE from 1986 to 1998 was carried out by Winger from 1986 to 1989 and by Winter and Alston from 1989 to 1998. The fundamental processes of electron transfer, ionization, and excitation in ion-ion, ion-atom, and, more recently, ion-molecule collisions were addressed. These collision processes were treated in the context of simple one-electron, quasi-one-electron, or two-electron systems in order to provide unambiguous results and reveal more clearly the collisional mechanisms. Winter`s work generally focused on the intermediate projectile-energy range corresponding to proton energies from about ten to a few hundred keV. In this velocity-matching energy range, the electron-transfer cross section reaches a peak, and many states, including electron-transfer and ionization states, contribute to the overall electron-cloud distribution and transition probabilities; a large number of states are coupled, and therefore perturbative approaches are generally inappropriate. These coupled-state calculations were sometimes also extended to higher energies to join with perturbative results. Alston concentrated on intermediate-energy asymmetric collision systems, for which coupling with the projectile is weaker, but many target states are included, and on high energies (MeV energies). Thus, while perturbation theory for electron transfer is valid, it is not adequate to first order. The studies by Winter and Alston described were often done in parallel. Alston also developed formal perturbative approaches not tied to any particular system. Materials studied included He{sup +}, Li{sup 2+}, Be{sup 3+}, B{sup 4+}, C{sup 5+}, and the H{sup +} + Na system.

  19. Diffusion-regulated phase-transfer catalysis for atom transfer radical polymerization of methyl methacrylate in an aqueous/organic biphasic system.

    Science.gov (United States)

    Ding, Mingqiang; Jiang, Xiaowu; Peng, Jinying; Zhang, Lifen; Cheng, Zhenping; Zhu, Xiulin

    2015-03-01

    A concept based on diffusion-regulated phase-transfer catalysis (DRPTC) in an aqueous-organic biphasic system with copper-mediated initiators for continuous activator regeneration is successfully developed for atom transfer radical polymerization (ICAR ATRP) (termed DRPTC-based ICAR ATRP here), using methyl methacrylate (MMA) as a model monomer, ethyl α-bromophenylacetate (EBrPA) as an initiator, and tris(2-pyridylmethyl)amine (TPMA) as a ligand. In this system, the monomer and initiating species in toluene (organic phase) and the catalyst complexes in water (aqueous phase) are simply mixed under stirring at room temperature. The trace catalyst complexes transfer into the organic phase via diffusion to trigger ICAR ATRP of MMA with ppm level catalyst content once the system is heated to the polymerization temperature (75 °C). It is found that well-defined PMMA with controlled molecular weights and narrow molecular weight distributions can be obtained easily. Furthermore, the polymerization can be conducted in the presence of limited amounts of air without using tedious degassed procedures. After cooling to room temperature, the upper organic phase is decanted and the lower aqueous phase is reused for another 10 recycling turnovers with ultra low loss of catalyst and ligand loading. At the same time, all the recycled catalyst complexes retain nearly perfect catalytic activity and controllability, indicating a facile and economical strategy for catalyst removal and recycling.

  20. Understanding the Atomic-Level Chemistry and Structure of Oxide Deposits on Fuel Rods in Light Water Nuclear Reactors Using First Principles Methods

    Science.gov (United States)

    Rak, Zs.; O'Brien, C. J.; Brenner, D. W.; Andersson, D. A.; Stanek, C. R.

    2016-09-01

    The results of recent studies are discussed in which first principles calculations at the atomic level have been used to expand the thermodynamic database for science-based predictive modeling of the chemistry, composition and structure of unwanted oxides that deposit on the fuel rods in pressurized light water nuclear reactors. Issues discussed include the origin of the particles that make up deposits, the structure and properties of the deposits, and the forms by which boron uptake into the deposits can occur. These first principles approaches have implications for other research areas, such as hydrothermal synthesis and the stability and corrosion resistance of other materials under other extreme conditions.

  1. Merit of ground-state electronegativities; a reply to ``Comments on `Introduction to the chemistry of fractionally charged atoms: Electronegativity' ''

    Science.gov (United States)

    Lackner, Klaus S.; Zweig, George

    1987-09-01

    The arguments presented in the Comment by Liebman and Huheey are shown to be incorrect. The operational equivalence of Mulliken ground-state electronegativities and Pauling electronegativities is demonstrated for neutral atoms. It is shown that ground-state electronegativities and valence-state electronegativities for both neutral atoms and ions are also operationally equivalent. A single electronegativity scale based on Mulliken ground-state electronegativities may therefore be used for neutral atoms, ions, and fractionally charged atoms, as originally implied in the paper by Lackner and Zweig.

  2. Rydberg Matter clusters of alkali metal atoms: the link between meteoritic matter, polar mesosphere summer echoes (PMSE), sporadic sodium layers, polar mesospheric clouds (PMCs, NLCs), and ion chemistry

    CERN Document Server

    Olofson, Frans; Holmlid, Leif

    2010-01-01

    A material exists which links together the influx of meteoritic matter from interplanetary space, the polar mesosphere summer echoes (PMSE), the sporadic sodium layers, the polar mesospheric clouds (PMCs, NLCs), and the observed ion chemistry in the mesosphere. The evidence in these research fields is here analyzed and found to agree well with the properties of Rydberg Matter (RM). This material has been studied with numerous methods in the laboratory. Alkali atoms, mainly Na, reach the mesosphere in the form of interplanetary (meteoritic, cometary) dust. The planar RM clusters NaN usually contain N = 19, 37 or 61 atoms, and have the density of air at 90 km altitude where they float. The diameters of the clusters are 10-100 nm from laboratory high precision radio frequency spectroscopic studies. Such experiments show that RM clusters interact strongly with radar frequencies: this explains the radio frequency heating and reflection studies of PMSE layers. The clusters give the low temperature in the mesosphere...

  3. Web-based computational chemistry education with CHARMMing III: Reduction potentials of electron transfer proteins.

    Science.gov (United States)

    Perrin, B Scott; Miller, Benjamin T; Schalk, Vinushka; Woodcock, H Lee; Brooks, Bernard R; Ichiye, Toshiko

    2014-07-01

    A module for fast determination of reduction potentials, E°, of redox-active proteins has been implemented in the CHARMM INterface and Graphics (CHARMMing) web portal (www.charmming.org). The free energy of reduction, which is proportional to E°, is composed of an intrinsic contribution due to the redox site and an environmental contribution due to the protein and solvent. Here, the intrinsic contribution is selected from a library of pre-calculated density functional theory values for each type of redox site and redox couple, while the environmental contribution is calculated from a crystal structure of the protein using Poisson-Boltzmann continuum electrostatics. An accompanying lesson demonstrates a calculation of E°. In this lesson, an ionizable residue in a [4Fe-4S]-protein that causes a pH-dependent E° is identified, and the E° of a mutant that would test the identification is predicted. This demonstration is valuable to both computational chemistry students and researchers interested in predicting sequence determinants of E° for mutagenesis.

  4. Web-based computational chemistry education with CHARMMing III: Reduction potentials of electron transfer proteins.

    Directory of Open Access Journals (Sweden)

    B Scott Perrin

    2014-07-01

    Full Text Available A module for fast determination of reduction potentials, E°, of redox-active proteins has been implemented in the CHARMM INterface and Graphics (CHARMMing web portal (www.charmming.org. The free energy of reduction, which is proportional to E°, is composed of an intrinsic contribution due to the redox site and an environmental contribution due to the protein and solvent. Here, the intrinsic contribution is selected from a library of pre-calculated density functional theory values for each type of redox site and redox couple, while the environmental contribution is calculated from a crystal structure of the protein using Poisson-Boltzmann continuum electrostatics. An accompanying lesson demonstrates a calculation of E°. In this lesson, an ionizable residue in a [4Fe-4S]-protein that causes a pH-dependent E° is identified, and the E° of a mutant that would test the identification is predicted. This demonstration is valuable to both computational chemistry students and researchers interested in predicting sequence determinants of E° for mutagenesis.

  5. Tandem catalysis of ring-closing metathesis/atom transfer radical reactions with homobimetallic ruthenium–arene complexes

    Directory of Open Access Journals (Sweden)

    Yannick Borguet

    2010-12-01

    Full Text Available The tandem catalysis of ring-closing metathesis/atom transfer radical reactions was investigated with the homobimetallic ruthenium–indenylidene complex [(p-cymeneRu(μ-Cl3RuCl(3-phenyl-1-indenylidene(PCy3] (1 to generate active species in situ. The two catalytic processes were first carried out independently in a case study before the whole sequence was optimized and applied to the synthesis of several polyhalogenated bicyclic γ-lactams and lactones from α,ω-diene substrates bearing trihaloacetamide or trichloroacetate functionalities. The individual steps were carefully monitored by 1H and 31P NMR spectroscopies in order to understand the intimate details of the catalytic cycles. Polyhalogenated substrates and the ethylene released upon metathesis induced the clean transformation of catalyst precursor 1 into the Ru(II–Ru(III mixed-valence compound [(p-cymeneRu(μ-Cl3RuCl2(PCy3], which was found to be an efficient promoter for atom transfer radical reactions under the adopted experimental conditions.

  6. An improved experimental databank of transferable multipolar atom models--ELMAM2. Construction details and applications.

    Science.gov (United States)

    Domagała, Sławomir; Fournier, Bertrand; Liebschner, Dorothee; Guillot, Benoît; Jelsch, Christian

    2012-05-01

    ELMAM2 is a generalized and improved library of experimentally derived multipolar atom types. The previously published ELMAM database is restricted mostly to protein atoms. The current database is extended to common functional groups encountered in organic molecules and is based on optimized local axes systems taking into account the local pseudosymmetry of the molecular fragment. In this approach, the symmetry-restricted multipoles have zero populations, while others take generally significant values. The various applications of the database are described. The deformation electron densities, electrostatic potentials and interaction energies calculated for several tripeptides and aromatic molecules are calculated using ELMAM2 electron-density parameters and compared with the former ELMAM database and density functional theory calculations.

  7. Comparison of static and microfluidic protease assays using modified bioluminescence resonance energy transfer chemistry.

    Directory of Open Access Journals (Sweden)

    Nan Wu

    Full Text Available BACKGROUND: Fluorescence and bioluminescence resonance energy transfer (F/BRET are two forms of Förster resonance energy transfer, which can be used for optical transduction of biosensors. BRET has several advantages over fluorescence-based technologies because it does not require an external light source. There would be benefits in combining BRET transduction with microfluidics but the low luminance of BRET has made this challenging until now. METHODOLOGY: We used a thrombin bioprobe based on a form of BRET (BRET(H, which uses the BRET(1 substrate, native coelenterazine, with the typical BRET(2 donor and acceptor proteins linked by a thrombin target peptide. The microfluidic assay was carried out in a Y-shaped microfluidic network. The dependence of the BRET(H ratio on the measurement location, flow rate and bioprobe concentration was quantified. Results were compared with the same bioprobe in a static microwell plate assay. PRINCIPAL FINDINGS: The BRET(H thrombin bioprobe has a lower limit of detection (LOD than previously reported for the equivalent BRET(1-based version but it is substantially brighter than the BRET(2 version. The normalised BRET(H ratio of the bioprobe changed 32% following complete cleavage by thrombin and 31% in the microfluidic format. The LOD for thrombin in the microfluidic format was 27 pM, compared with an LOD of 310 pM, using the same bioprobe in a static microwell assay, and two orders of magnitude lower than reported for other microfluidic chip-based protease assays. CONCLUSIONS: These data demonstrate that BRET based microfluidic assays are feasible and that BRET(H provides a useful test bed for optimising BRET-based microfluidics. This approach may be convenient for a wide range of applications requiring sensitive detection and/or quantification of chemical or biological analytes.

  8. Analysis of Ligand-Receptor Association and Intermediate Transfer Rates in Multienzyme Nanostructures with All-Atom Brownian Dynamics Simulations.

    Science.gov (United States)

    Roberts, Christopher C; Chang, Chia-En A

    2016-08-25

    We present the second-generation GeomBD Brownian dynamics software for determining interenzyme intermediate transfer rates and substrate association rates in biomolecular complexes. Substrate and intermediate association rates for a series of enzymes or biomolecules can be compared between the freely diffusing disorganized configuration and various colocalized or complexed arrangements for kinetic investigation of enhanced intermediate transfer. In addition, enzyme engineering techniques, such as synthetic protein conjugation, can be computationally modeled and analyzed to better understand changes in substrate association relative to native enzymes. Tools are provided to determine nonspecific ligand-receptor association residence times, and to visualize common sites of nonspecific association of substrates on receptor surfaces. To demonstrate features of the software, interenzyme intermediate substrate transfer rate constants are calculated and compared for all-atom models of DNA origami scaffold-bound bienzyme systems of glucose oxidase and horseradish peroxidase. Also, a DNA conjugated horseradish peroxidase enzyme was analyzed for its propensity to increase substrate association rates and substrate local residence times relative to the unmodified enzyme. We also demonstrate the rapid determination and visualization of common sites of nonspecific ligand-receptor association by using HIV-1 protease and an inhibitor, XK263. GeomBD2 accelerates simulations by precomputing van der Waals potential energy grids and electrostatic potential grid maps, and has a flexible and extensible support for all-atom and coarse-grained force fields. Simulation software is written in C++ and utilizes modern parallelization techniques for potential grid preparation and Brownian dynamics simulation processes. Analysis scripts, written in the Python scripting language, are provided for quantitative simulation analysis. GeomBD2 is applicable to the fields of biophysics, bioengineering

  9. Synthesis, characterisation, and oxygen atom transfer reactions involving the first gold(I)-alkylperoxo complexes.

    Science.gov (United States)

    Collado, Alba; Gómez-Suárez, Adrián; Oonishi, Yoshihiro; Slawin, Alexandra M Z; Nolan, Steven P

    2013-11-25

    The synthesis of a new class of organogold species containing a peroxo moiety is reported. Complexes [Au(IPr)(OO(t)Bu)] and [Au(SIPr)(OO(t)Bu)] have been synthesised via a straightforward methodology using the parent gold(I) hydroxide complexes as synthons. These complexes have been successfully used in oxygen-transfer reactions to triphenylphosphine.

  10. Modelling of the heat transfer during oxygen atoms recombination on metallic surfaces in a plasma reactor

    NARCIS (Netherlands)

    Cavadias, S; Cauquot, P; Amouroux, J

    1997-01-01

    Space shuttle overheating during the re-entry phase, due to catalytic oxygen recombination on the thermal protection system, is a problem of practical and theoretical interest. The energy transfer is characterised by the product of the accommodation and the recombination coefficients. Previous measu

  11. Back-Influence of Molecular Motion on Energy Transfer in the Landau-Teller Model of Atom Molecule Scattering.

    Science.gov (United States)

    Pollak, Eli

    2016-07-21

    This year we celebrate the 80th anniversary of the Landau-Teller model for energy exchange in a collinear collision of an atom with a harmonic diatomic molecule. Even after 80 years though, the analytic theory to date has not included in it the back-influence of the oscillator's motion on the energy transfer between the approaching particle and the molecule. This is the topic of the present paper. The back-influence can be obtained by employing classical second-order perturbation theory. The second-order theory is used in both a classical and semiclassical context. Classically, analytic expressions are derived for the final phase and action of the diatom, after the collision. The energy loss of the atom is shown to decrease linearly with the increasing energy of the oscillator. The magnitude of this decrease is a direct consequence of the back-reaction of the oscillator on the translational motion. The qualitative result is universal, in the sense that it is not dependent on the details of the interaction of the atom with the oscillator. A numerical application to a model collision of an Ar atom with a Br2 diatom demonstrates the importance and accuracy of the second-order perturbation theory. The same results are then used to derive a second-order perturbation theory semiclassical expression for the quantum transition probability from initial vibrational state ni to final vibrational state nf of the oscillator. A comparison of the theory with exact quantum data is presented for a model collision of Br2 with a hydrogen molecule, where the hydrogen molecule is considered as a single approaching particle.

  12. 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,

  13. Simulation of lean NOx trap performance with microkinetic chemistry and without mass transfer.

    Energy Technology Data Exchange (ETDEWEB)

    Larson, Rich; Daw, C. Stuart (Oak Ridge National Laboratory, Knoxville, TN); Pihl, Josh A. (Oak Ridge National Laboratory, Knoxville, TN); Chakravarthy, V. Kalyana (Oak Ridge National Laboratory, Knoxville, TN)

    2011-08-01

    A microkinetic chemical reaction mechanism capable of describing both the storage and regeneration processes in a fully formulated lean NO{sub x} trap (LNT) is presented. The mechanism includes steps occurring on the precious metal, barium oxide (NO{sub x} storage), and cerium oxide (oxygen storage) sites of the catalyst. The complete reaction set is used in conjunction with a transient plug flow reactor code to simulate not only conventional storage/regeneration cycles with a CO/H{sub 2} reductant, but also steady flow temperature sweep experiments that were previously analyzed with just a precious metal mechanism and a steady state code. The results show that NO{sub x} storage is not negligible during some of the temperature ramps, necessitating a re-evaluation of the precious metal kinetic parameters. The parameters for the entire mechanism are inferred by finding the best overall fit to the complete set of experiments. Rigorous thermodynamic consistency is enforced for parallel reaction pathways and with respect to known data for all of the gas phase species involved. It is found that, with a few minor exceptions, all of the basic experimental observations can be reproduced with these purely kinetic simulations, i.e., without including mass-transfer limitations. In addition to accounting for normal cycling behavior, the final mechanism should provide a starting point for the description of further LNT phenomena such as desulfation and the role of alternative reductants.

  14. Nobody Can See Atoms: Science Camps Highlighting Approaches for Making Chemistry Accessible to Blind and Visually Impaired Students

    Science.gov (United States)

    Wedler, Henry B.; Boyes, Lee; Davis, Rebecca L.; Flynn, Dan; Franz, Annaliese; Hamann, Christian S.; Harrison, Jason G.; Lodewyk, Michael W.; Milinkevich, Kristin A.; Shaw, Jared T.; Tantillo, Dean J.; Wang, Selina C.

    2014-01-01

    Curricula for three chemistry camp experiences for blind and visually impaired (BVI) individuals that incorporated single- and multiday activities and experiments accessible to BVI students are described. Feedback on the camps from students, mentors, and instructors indicates that these events allowed BVI students, who in many cases have been…

  15. The Development of Dalton's Atomic Theory as a Case Study in the History of Science: Reflections for Educators in Chemistry

    Science.gov (United States)

    Viana, Helio Elael Bonini; Porto, Paulo Alves

    2010-01-01

    The inclusion of the history of science in science curricula--and specially, in the curricula of science teachers--is a trend that has been followed in several countries. The reasons advanced for the study of the history of science are manifold. This paper presents a case study in the history of chemistry, on the early developments of John…

  16. Experiences and Reflections about Teaching Atomic Structure in a Jigsaw Classroom in Lower Secondary School Chemistry Lessons

    Science.gov (United States)

    Eilks, Ingo

    2005-01-01

    The study investigates the students opinions on learning in a jigsaw classroom and enquiring on what they think about jigsaw classroom having the potential to make chemistry learning more attractive and whether it can help them to improve their communicative and social skills. The study was carried out using a lesson design for teaching an…

  17. The Development of Dalton's Atomic Theory as a Case Study in the History of Science: Reflections for Educators in Chemistry

    Science.gov (United States)

    Viana, Helio Elael Bonini; Porto, Paulo Alves

    2010-01-01

    The inclusion of the history of science in science curricula--and specially, in the curricula of science teachers--is a trend that has been followed in several countries. The reasons advanced for the study of the history of science are manifold. This paper presents a case study in the history of chemistry, on the early developments of John…

  18. Ionization and charge transfer in high-energy ion-atom collisions

    Energy Technology Data Exchange (ETDEWEB)

    Schlachter, A.S.; Berkner, K.H.; Stearns, J.W.; Schmidt-Boecking, H.; Kelbch, S.; Ullrich, J.; Hagmann, S.; Richard, P.; Stockli, M.P.; Graham, W.G.

    1986-11-01

    Electron capture and loss by fast highly charged ions in a gas target, and ionization of the target by passage of the fast projectile beam, are fundamental processes in atomic physics. These processes, along with excitation, can be experimentally studied separately (''singles'') or together (''coincidence''). This paper is a review of recent results on singles measurements for electron capture and loss and for target ionization, for velocities which are generally high relative to the active electron, including recent ionization measurements for a nearly relativistic projectile. 11 refs., 6 figs.

  19. Heat Transfer Salts for Nuclear Reactor Systems - Chemistry Control, Corrosion Mitigation, and Modeling

    Energy Technology Data Exchange (ETDEWEB)

    Anderson, Mark [Univ. of Wisconsin, Madison, WI (United States); Sridharan, Kumar [Univ. of Wisconsin, Madison, WI (United States); Morgan, Dane [Univ. of Wisconsin, Madison, WI (United States); Peterson, Per [Univ. of Wisconsin, Madison, WI (United States); Calderoni, Pattrick [Univ. of Wisconsin, Madison, WI (United States); Scheele, Randall [Univ. of Wisconsin, Madison, WI (United States); Casekka, Andrew [Univ. of Wisconsin, Madison, WI (United States); McNamara, Bruce [Univ. of Wisconsin, Madison, WI (United States)

    2015-01-22

    -evaluate thermophysical properties of flibe and flinak. Pacific Northwest National Laboratories has focused on evaluating the fluorinating gas nitrogen trifluoride as a potential salt purification agent. Work there was performed on removing hydroxides and oxides from flinak salt under controlled conditions. Lastly, the University of California Berkeley has spent considerable time designing and simulating reactor components with fluoride salts at high temperatures. Despite the hurdles presented by the innate chemical hazards, considerable progress has been made. The stage has been set to perform new research on salt chemical control which could advance the fluoride salt cooled reactor concept towards commercialization. What were previously thought of as chemical undesirable, but nuclear certified, alloys have been shown to be theoretically compatible with fluoride salts at high temperatures. This preliminary report has been prepared to communicate the construction of the basic infrastructure required for flibe, as well as suggest original research to performed at the University of Wisconsin. Simultaneously, the contents of this report can serve as a detailed, but introductory guide to allow anyone to learn the fundamentals of chemistry, engineering, and safety required to work with flibe salt.

  20. Human frataxin activates Fe-S cluster biosynthesis by facilitating sulfur transfer chemistry.

    Science.gov (United States)

    Bridwell-Rabb, Jennifer; Fox, Nicholas G; Tsai, Chi-Lin; Winn, Andrew M; Barondeau, David P

    2014-08-05

    Iron-sulfur clusters are ubiquitous protein cofactors with critical cellular functions. The mitochondrial Fe-S assembly complex, which consists of the cysteine desulfurase NFS1 and its accessory protein (ISD11), the Fe-S assembly protein (ISCU2), and frataxin (FXN), converts substrates l-cysteine, ferrous iron, and electrons into Fe-S clusters. The physiological function of FXN has received a tremendous amount of attention since the discovery that its loss is directly linked to the neurodegenerative disease Friedreich's ataxia. Previous in vitro results revealed a role for human FXN in activating the cysteine desulfurase and Fe-S cluster biosynthesis activities of the Fe-S assembly complex. Here we present radiolabeling experiments that indicate FXN accelerates the accumulation of sulfur on ISCU2 and that the resulting persulfide species is viable in the subsequent synthesis of Fe-S clusters. Additional mutagenesis, enzyme kinetic, UV-visible, and circular dichroism spectroscopic studies suggest conserved ISCU2 residue C104 is critical for FXN activation, whereas C35, C61, and C104 are all essential for Fe-S cluster formation on the assembly complex. These results cannot be fully explained by the hypothesis that FXN functions as an iron donor for Fe-S cluster biosynthesis, and further support an allosteric regulator role for FXN. Together, these results lead to an activation model in which FXN accelerates persulfide formation on NFS1 and favors a helix-to-coil interconversion on ISCU2 that facilitates the transfer of sulfur from NFS1 to ISCU2 as an initial step in Fe-S cluster biosynthesis.

  1. Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

    Science.gov (United States)

    de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

    2017-03-24

    We report the synthesis, characterization, and reactivity of [LFe3 (PhPz)3 OMn((s) PhIO)][OTf]x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, (57) Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe(III)2 Fe(II) Mn(II) vs. Fe(III)3 Mn(II) ) influence oxygen atom transfer in tetranuclear Fe3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.

  2. NARROW-DISPERSED CROSSLINKED CORE-SHELL POLYMER MICROSPHERES PREPARED BY SURFACE-INITIATED ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Yu-zeng Zhao; Xin-lin Yang; Feng Bai; Wen-qiang Huang

    2005-01-01

    Grafting of polystyrene with narrowly dispersed polymer microspheres through surface-initiated atom transfer radical polymerization (ATRP) was investigated. Polydivinylbenzene (PDVB) microspheres were prepared by dispersion polymerization with poly(N-vinyl pyrrolidone) (PVP) as stabilizer. The surfaces of PDVB microspheres were chloromethylated by chloromethyl methyl ether in the presence of zinc chloride as catalyst to form chloromethylbenzene initiating core sites for subsequent ATRP grafting of styrene using CuC1/bpy as catalytic system. Polystyrene was found to be grafted not only from the particle surfaces but also from within a thin shell layer, resulting in the formation of particles size increased from 2.38-2.58 μm, which can further grow to 2.93 μm during secondary grafting polymerization of styrene. This demonstrates that grafting polymerization proceeds through a typical ATRP procedure with living nature. All of the prepared microspheres have narrow particle size distribution with coefficient of variation around 10%.

  3. Development of atom transfer radical polymer-modified gold nanoparticle-based enzyme-linked immunosorbent assay (ELISA).

    Science.gov (United States)

    Chen, Feng; Hou, Shike; Li, Qingsheng; Fan, Haojun; Fan, Rong; Xu, Zhongwei; Zhala, Gahu; Mai, Xia; Chen, Xiaoyi; Chen, Xuyi; Liu, Yingfu

    2014-10-21

    In this work, a novel enzyme-linked immunosorbent assay (ELISA) with a low limit of detection and high sensitivity was developed using atom transfer radical polymer (ATRP)-modified gold nanoparticles (AuNPs). Clear signal amplification was achieved by introducing an abundance of horseradish peroxidase (HRP) to the AuNPs, because of the ATRP modification. This result suggested that the new ELISA was able to detect antigens in complex mixtures, and the limit of detection (LOD) was lower than that of conventional ELISA by a factor of 81. The new ELISA strategy greatly decreased the LOD during analysis and exhibited excellent reproducibility, stability, and feasibility. Therefore, it is a promising technique with many potential applications in biochemistry and medical science research.

  4. Highly selective capture of nucleosides with boronic acid functionalized polymer brushes prepared by atom transfer radical polymerization.

    Science.gov (United States)

    Cheng, Ting; Zhu, Shuqiang; Zhu, Bin; Liu, Xiaoyan; Zhang, Haixia

    2016-04-01

    The nucleoside or modified nucleoside level in biological fluids reflects the pathological or physiological state of the body. Boronate affinity absorbents are widely used to selectively extract nucleosides from complex samples. In this work, a novel functionalized absorbent was synthesized by attaching 4-mercaptophenylboronic acid to gold nanoparticles on modified attapulgite. The surface of the attapulgite was modified by poly(acryloyloxyethyltrimethyl ammonium chloride) by atom transfer radical polymerization, creating many polymer brushes on the surface. The resultant material exhibited superior binding capacity (30.83 mg/g) for adenosine and was able to capture cis-diol nucleosides from 1000-fold interferences. Finally, to demonstrate its potential for biomolecule extraction, this boronate affinity material was used to preconcentrate nucleosides from human urine and plasma.

  5. Visible Light-Induced Metal Free Surface Initiated Atom Transfer Radical Polymerization of Methyl Methacrylate on SBA-15

    Directory of Open Access Journals (Sweden)

    Liang Ma

    2017-02-01

    Full Text Available Surface-initiated atom transfer radical polymerization (SI-ATRP is one of the most versatile techniques to modify the surface properties of materials. Recent developed metal-free SI-ATRP makes such techniques more widely applicable. Herein photo-induced metal-free SI-ATRP of methacrylates, such as methyl methacrylate, N-isopropanyl acrylamide, and N,N-dimethylaminoethyl methacrylate, on the surface of SBA-15 was reported to fabricate organic-inorganic hybrid materials. A SBA-15-based polymeric composite with an adjustable graft ratio was obtained. The structure evolution during the SI-ATRP modification of SBA-15 was monitored and verified by FT-IR, XPS, TGA, BET, and TEM. The obtained polymeric composite showed enhanced adsorption ability for the model compound toluene in aqueous conditions. This procedure provides a low-cost, readily available, and easy modification method to synthesize polymeric composites without the contamination of metal.

  6. Bottom-Up Fabrication of Nanopatterned Polymers on DNA Origami by In Situ Atom-Transfer Radical Polymerization.

    Science.gov (United States)

    Tokura, Yu; Jiang, Yanyan; Welle, Alexander; Stenzel, Martina H; Krzemien, Katarzyna M; Michaelis, Jens; Berger, Rüdiger; Barner-Kowollik, Christopher; Wu, Yuzhou; Weil, Tanja

    2016-05-04

    Bottom-up strategies to fabricate patterned polymers at the nanoscale represent an emerging field in the development of advanced nanodevices, such as biosensors, nanofluidics, and nanophotonics. DNA origami techniques provide access to distinct architectures of various sizes and shapes and present manifold opportunities for functionalization at the nanoscale with the highest precision. Herein, we conduct in situ atom-transfer radical polymerization (ATRP) on DNA origami, yielding differently nanopatterned polymers of various heights. After cross-linking, the grafted polymeric nanostructures can even stably exist in solution without the DNA origami template. This straightforward approach allows for the fabrication of patterned polymers with low nanometer resolution, which provides access to unique DNA-based functional hybrid materials.

  7. Lewis‐Acid‐assisted Hydrogen Atom Transfer to Manganese(V)‐Oxo Corrole through Valence Tautomerization

    OpenAIRE

    Bougher, Curt J.; Abu‐Omar, Mahdi M.

    2016-01-01

    Abstract The kinetics of formation of the valence tautomers (tpfc⋅)MnIV(O−LA)] n+ [where LA=ZnII, CaII, ScIII, YbIII, B(C6F5)3, and trifluoroacetic acid (TFA); tpfc=5,10,15‐tris(pentafluorophenyl) corrole] from (tpfc)MnV(O) were followed by UV/Vis spectroscopy, giving second‐order rate constants ranging over five orders of magnitude from 10−2 for Ca to 103  m −1 s−1 for Sc. Hydrogen atom transfer (HAT) rates from 2,4‐di‐tert‐butyl phenol (2,4‐DTBP) to the various Lewis acid valence tautomers ...

  8. Inner hydrogen atom transfer in benzo-fused low symmetrical metal-free tetraazaporphyrin and phthalocyanine analogues: density functional theory studies.

    Science.gov (United States)

    Qi, Dongdong; Zhang, Yuexing; Cai, Xue; Jiang, Jianzhuang; Bai, Ming

    2009-02-01

    Density functional theory (DFT) calculations were carried out to study the inner hydrogen atom transfer in low symmetrical metal-free tetrapyrrole analogues ranging from tetraazaporphyrin H(2)TAP (A(0)B(0)C(0)D(0)) to naphthalocyanine H(2)Nc (A(2)B(2)C(2)D(2)) via phthalocyanine H(2)Pc (A(1)B(1)C(1)D(1)). All the transition paths of sixteen different compounds (A(0)B(0)C(0)D(0)-A(2)B(2)C(2)D(2) and A(0)B(0)C(m)D(n), m rings onto the TAP skeleton have significant effect on the potential energy barrier of the inner hydrogen atom transfer. Introducing fused benzene rings onto the hydrogen-releasing pyrrole rings can increase the transitivity of inner hydrogen atom and thus lower the transfer barrier of this inner hydrogen atom while fusing benzene rings onto the hydrogen-accepting pyrrole rings will increase the hydrogen transfer barrier to this pyrrole ring. The transient cis-isomer intermediate with hydrogen atoms joined to the two adjacent pyrrole rings with less fused benzene rings is much stable than the others. It is also found that the benzene rings fused directly onto pyrrole rings have more effect on the inner hydrogen atom transfer than the outer benzene rings fused onto the periphery of isoindole rings. The present work, representing the first effort towards systematically understanding the effect of ring enlargement through asymmetrical peripheral fusion of benzene ring(s) onto the TAP skeleton on the inner hydrogen transfer of tetrapyrrole derivatives, will be helpful in clarifying the N-H tautomerization phenomenon and detecting the cis-porphyrin isomer in bio-systems.

  9. SYNTHESIS OF POLY(METHYL METHACRYLATE)-graft-POLYSTYRENE BY ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Sheng-min Gong; Qun-sheng Li; Yan Shi; Zhi-feng Fu; Shu-ke Jiao; Wan-tai Yang

    2003-01-01

    The radical copolymerization of methyl methacrylate and 2-hydroxyethyl methacrylate was carried out via atom complex. This polymerization proceeds in a living fashion with controlled molecular weight and low polydispersity. The obtained copolymer was esterified with 2-bromoisobutylryl bromide yielding a macroinitiator, poly(methyl methacrylate-co-2-hydroxyethyl methacrylate-co-2-(2-bromoisobutyryloxy)ethyl methacrylate), and its structure was characterized by 1HNMR. This macroinitiator was used for ATRP of styrene to synthesize poly(methyl methacrylate)-grafi-polystyrene. The molecular weight of graft copolymer increased with the monomer conversion, and the polydispersity remained relatively low.The individual grafted polystyrene chains were cleaved from the macroinitiator backbone by hydrolysis and the hydrolyzed product was characterized by 1H-NMR and GPC.

  10. Eikonal approximation for charge transfer from a multielectron atom to fast projectiles

    Science.gov (United States)

    Ho, T. S.; Lieber, M.; Chan, F. T.; Omidvar, K.

    1981-01-01

    The eikonal approach developed previously for calculating electron-capture cross sections for bare projectiles colliding with hydrogenic targets is extended here to allow for multielectron targets. Both the impact and wave pictures are employed and their equivalence is discussed. As a first approximation, each atomic orbital is specified by the three hydrogenic quantum numbers, an effective nuclear charge Z sub t, and an energy eigenvalue in the impact picture, or ionization potential in the wave picture. The Z sub t prime appearing in the eikonal phase factor is left undetermined because of incomplete information on the many-body target. However, analytic expressions are derived for the theoretical cross sections, and numerical values are calculated for simple choices of Z sub t prime. Those results are compared with existing experimental data for C, Ne, Ar, N2, O2, and He targets.

  11. Charge transfer on porous silicon membranes studied by current-sensing atomic force microscopy

    Institute of Scientific and Technical Information of China (English)

    Bing Xia; Qiang Miao; Jie Chao; Shou Jun Xiao; Hai Tao Wang; Zhong Dang Xiao

    2008-01-01

    A visible rectification effect on the current-voltage curves of metal/porous silicon/p-silicon has been observed by currentsensing atomic force microscopy.The current-voltage curves of porous silicon membranes with different porosities,prepared through variation of etching current density for a constant time,indicate that a higher porosity results in a higher resistance and thus a lower rectification,until the current reaches a threshold at a porosity>55%.We propose that the conductance mode in the porous silicon membrane with porosities>55% is mainly a hopping mechanism between nano-crystallites and an inverse static electric field between the porous silicon and p-Si interface blocks the electron injection from porous silicon to p-Si,but with porosities <55%,electron flows through a direct continuous channel between nano-crystallites.

  12. Protein-resistant polyurethane via surface-initiated atom transfer radical polymerization of oligo(ethylene glycol) methacrylate.

    Science.gov (United States)

    Jin, Zhilin; Feng, Wei; Zhu, Shiping; Sheardown, Heather; Brash, John L

    2009-12-15

    Protein-resistant polyurethane (PU) surfaces were prepared by surface-initiated simultaneous normal and reverse atom transfer radical polymerization (s-ATRP) of poly(oligo(ethylene glycol) methacrylate) (poly (OEGMA)). Oxygen plasma treatment was employed for initial activation of the PU surface. The grafted polymer chain length was adjusted by varying the molar ratio of monomer to sacrificial initiator in solution from 5:1 to 200:1. The modified PU surfaces were characterized by water contact angle, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Protein adsorption experiments from tris-buffered saline (TBS) and plasma were carried out to evaluate the protein-resistance of the surfaces. Adsorption from single and binary protein solutions as well as from plasma was significantly reduced after modification. Adsorption decreased with increasing poly(OEGMA) chain length. Fibrinogen (Fg) adsorption on the 200:1 monomer/initiator surface was in the range of 3-33 ng/cm(2) representing 96-99% reduction compared with the unmodified PU. Fg adsorption from 0.01-10% plasma was as low as 1-5 ng/cm(2). Moreover, binary protein adsorption experiments using Fg and lysozyme (Lys) showed that protein size is a factor in the protein resistance of these surfaces.

  13. Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Jingjing, E-mail: jjwang1@hotmail.com; Wei, Jun

    2016-09-30

    Highlights: • Crosslinked hydrogel brushes were grafted from SS surfaces for marine antifouling. • All brush-coated SS surfaces could effectively reduce the adhesion of biofouling. • The antifouling efficacy increased with the crosslinking density of hydrogels. - Abstract: Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

  14. Hydrogel brushes grafted from stainless steel via surface-initiated atom transfer radical polymerization for marine antifouling

    Science.gov (United States)

    Wang, Jingjing; Wei, Jun

    2016-09-01

    Crosslinked hydrogel brushes were grafted from stainless steel (SS) surfaces for marine antifouling. The brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC) and poly(ethylene glycol) methyl ether methacrylate (PEGMA) respectively with different fractions of crosslinker in the feed. The grafted layers prepared with different thickness were characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), ellipsometry and water contact angle measurements. With the increase in the fraction of crosslinker in the feed, the thickness of the grafted layer increased and the surface became smooth. All the brush-coated SS surfaces could effectively reduce the adhesion of bacteria and microalgae and settlement of barnacle cyprids, as compared to the pristine SS surface. The antifouling efficacy of the PEGMA polymer (PPEGMA)-grafted surface was higher than that of the MPC polymer (PMPC)-grafted surfaces. Furthermore, the crosslinked hydrogel brush-grafted surfaces exhibited better fouling resistance than the non-crosslinked polymer brush-grafted surfaces, and the antifouling efficacy increased with the crosslinking density. These hydrogel coatings of low toxicity and excellent anti-adhesive characteristics suggested their useful applications as environmentally friendly antifouling coatings.

  15. Hyperspherical elliptic coordinates treatment of muon transfer from muonic hydrogen to atomic oxygen

    CERN Document Server

    Dupays, A; Beswick, J A; Rizzo, C; Bakalov, D; Dupays, Arnaud; Lepetit, Bruno; Rizzo, Carlo; Bakalov, Dimitar

    2003-01-01

    Quantum-mechanical calculations of muon transfer between muonic hydrogen and an oxygen nuclei for $s$ waves and collision energies in the range $10^{-3} - 10^3$ eV, are presented. Close-coupling time-independent Schr\\"odinger equations, written in terms of hyperspherical elliptic coordinates were integrated along the hyper-radius to obtain the partial and total muon-transfer probabilities. The results show the expected Wigner-Bethe threshold behavior up to collision energies of the order of $10^{-2}$ eV and pronounced maxima at $10^2$ eV which can be interpreted in terms of crossings between potential energy curves corresponding to the entrance channel state $(\\mu p)_{1s} + \\mO$ and two product channels which asymptotically correlate to $p + (\\mO\\mu)_{n=5,6}$. The population of the final states with different orbital angular momenta is found to be essentially independent of energy in the range considered in this work. This can be attributed to a strong selection rule for the conservation of the quantum number...

  16. Comments on ''Introduction to the chemistry of fractionally charged atoms: Electronegativity''

    Energy Technology Data Exchange (ETDEWEB)

    Liebman, J.F.; Huheey, J.E.

    1987-09-01

    A comparison is made between the electronegativities of ''quark atoms'' as predicted by a recent article, and those suggested by traditional chemical methods. It is shown that the neglect of valence-state considerations for the ionization energies and electron affinities produces serious errors in calculating electronegativities by the Mulliken method. As analyses of the values for ''normal atoms'' show such disparities, it is likely that the new numbers are in error.

  17. Unification of Anion Relay Chemistry (ARC) with the Takeda and Hiyama Cross-Coupling Reactions: Identification of an Effective Silicon-Based Transfer Agent

    OpenAIRE

    Smith, Amos B.; Hoye, Adam T.; Martinez-Solorio, Dionicio; Kim, Won-Suk; Tong, Rongbiao

    2012-01-01

    The unification of Anion Relay Chemistry (ARC) with the Takeda and Hiyama palladium-mediated cross-coupling processes to provide aryl-aryl, alkenyl-aryl and alkenyl-alkenyl coupling products, exploiting a common silicon-based transfer agent, has been achieved. These results provide a practical solution to the intermolecular cross-coupling of organolithium reagents without problematic lithium-halogen exchange and/or undesired homocoupling that has kept organolithium cross-couplings from achiev...

  18. Interfacial Chemistry and the Design of Solid-Phase Nucleic Acid Hybridization Assays Using Immobilized Quantum Dots as Donors in Fluorescence Resonance Energy Transfer

    OpenAIRE

    Krull, Ulrich J.; W. Russ Algar

    2011-01-01

    The use of quantum dots (QDs) as donors in fluorescence resonance energy transfer (FRET) offer several advantages for the development of multiplexed solid-phase QD-FRET nucleic acid hybridization assays. Designs for multiplexing have been demonstrated, but important challenges remain in the optimization of these systems. In this work, we identify several strategies based on the design of interfacial chemistry for improving sensitivity, obtaining lower limits of detection (LOD) and enabling th...

  19. Cryo-EM structures and atomic model of the HIV-1 strand transfer complex intasome.

    Science.gov (United States)

    Passos, Dario Oliveira; Li, Min; Yang, Renbin; Rebensburg, Stephanie V; Ghirlando, Rodolfo; Jeon, Youngmin; Shkriabai, Nikoloz; Kvaratskhelia, Mamuka; Craigie, Robert; Lyumkis, Dmitry

    2017-01-06

    Like all retroviruses, HIV-1 irreversibly inserts a viral DNA (vDNA) copy of its RNA genome into host target DNA (tDNA). The intasome, a higher-order nucleoprotein complex composed of viral integrase (IN) and the ends of linear vDNA, mediates integration. Productive integration into host chromatin results in the formation of the strand transfer complex (STC) containing catalytically joined vDNA and tDNA. HIV-1 intasomes have been refractory to high-resolution structural studies. We used a soluble IN fusion protein to facilitate structural studies, through which we present a high-resolution cryo-electron microscopy (cryo-EM) structure of the core tetrameric HIV-1 STC and a higher-order form that adopts carboxyl-terminal domain rearrangements. The distinct STC structures highlight how HIV-1 can use the common retroviral intasome core architecture to accommodate different IN domain modules for assembly.

  20. Relativistic calculations of the K-K charge transfer and K-vacancy production probabilities in low-energy ion-atom collisions

    CERN Document Server

    Tupitsyn, I I; Shabaev, V M; Bondarev, A I; Deyneka, G B; Maltsev, I A; Hagmann, S; Plunien, G; Stoehlker, Th

    2011-01-01

    The previously developed technique for evaluation of charge-transfer and electron-excitation processes in low-energy heavy-ion collisions [I.I. Tupitsyn et al., Phys. Rev. A 82, 042701(2010)] is extended to collisions of ions with neutral atoms. The method employs the active electron approximation, in which only the active electron participates in the charge transfer and excitation processes while the passive electrons provide the screening DFT potential. The time-dependent Dirac wave function of the active electron is represented as a linear combination of atomic-like Dirac-Fock-Sturm orbitals, localized at the ions (atoms). The screening DFT potential is calculated using the overlapping densities of each ions (atoms), derived from the atomic orbitals of the passive electrons. The atomic orbitals are generated by solving numerically the one-center Dirac-Fock and Dirac-Fock-Sturm equations by means of a finite-difference approach with the potential taken as the sum of the exact reference ion (atom) Dirac-Fock...

  1. Single step synthesis of gold-amino acid composite, with the evidence of the catalytic hydrogen atom transfer (HAT) reaction, for the electrochemical recognition of Serotonin

    Science.gov (United States)

    Choudhary, Meenakshi; Siwal, Samarjeet; Nandi, Debkumar; Mallick, Kaushik

    2016-03-01

    A composite architecture of amino acid and gold nanoparticles has been synthesized using a generic route of 'in-situ polymerization and composite formation (IPCF)' [1,2]. The formation mechanism of the composite has been supported by a model hydrogen atom (H•≡H++e-) transfer (HAT) type of reaction which belongs to the proton coupled electron transfer (PCET) mechanism. The 'gold-amino acid composite' was used as a catalyst for the electrochemical recognition of Serotonin.

  2. Presenting the Bohr Atom.

    Science.gov (United States)

    Haendler, Blanca L.

    1982-01-01

    Discusses the importance of teaching the Bohr atom at both freshman and advanced levels. Focuses on the development of Bohr's ideas, derivation of the energies of the stationary states, and the Bohr atom in the chemistry curriculum. (SK)

  3. Acrylamide-b-N-isopropylacrylamide block copolymers : Synthesis by atomic transfer radical polymerization in water and the effect of the hydrophilic-hydrophobic ratio on the solution properties

    NARCIS (Netherlands)

    Wever, Diego Armando Z.; Ramalho, Graham; Picchioni, Francesco; Broekhuis, Antonius Augustinus

    2014-01-01

    A series of block copolymers of acrylamide and N-isopropylacrylamide (NIPAM) characterized by different ratios between the length of the two blocks have been prepared through atomic transfer radical polymerization in water at room temperature. The solution properties of the block copolymers were cor

  4. Shining Light on Copper: Unique Opportunities for Visible-Light-Catalyzed Atom Transfer Radical Addition Reactions and Related Processes.

    Science.gov (United States)

    Reiser, Oliver

    2016-09-20

    Visible-light photoredox catalysis offers exciting opportunities to achieve challenging carbon-carbon bond formations under mild and ecologically benign conditions. Desired features of photoredox catalysts are photostability, long excited-state lifetimes, strong absorption in the visible region, and high reduction or oxidation potentials to achieve electron transfer to substrates, thus generating radicals that can undergo synthetic organic transformations. These requirements are met in a convincing way by Ru(II)(phenanthroline)3- and Ir(III)(phenylpyridine)3-type complexes and, as a low-cost alternative, by organic dyes that offer a metal-free catalyst but suffer in general from lower photostability. Cu(I)(phenanthroline)2 complexes have been recognized for more than 30 years as photoresponsive compounds with highly negative Cu(I)* → Cu(II) oxidation potentials, but nevertheless, they have not been widely considered as suitable photoredox catalysts, mainly because their excited lifetimes are shorter by a factor of 5 to 10 compared with Ru(II) and Ir(III) complexes, their absorption in the visible region is weak, and their low Cu(II) → Cu(I) reduction potentials might impede the closure of a catalytic cycle for a given process. Contrasting again with Ru(II)L3 and Ir(III)L3 complexes, Cu(I)L2 assemblies undergo more rapid ligand exchange in solution, thus potentially reducing the concentration of the photoactive species. Focusing on atom transfer radical addition (ATRA) reactions and related processes, we highlight recent developments that show the utility of Cu(I)(phenanthroline)2 complexes as photoredox catalysts, demonstrating that despite their short excited-state lifetimes and weak absorption such complexes are efficient at low catalyst loadings. Moreover, some of the inherent disadvantages stated above can even be turned to advantages: (1) the low Cu(II) → Cu(I) reduction potential might efficiently promote reactions via a radical chain pathway, and (2

  5. Constructivist-Based Asynchronous Tutorial to Improve Transfer between Math and Chemistry Domains: Design, Implementation, and Analysis of the Impact of ReMATCH on General Chemistry Course Performance and Confidence

    Science.gov (United States)

    Barker, M. Danielle

    2011-07-01

    The two-year implementation of ReMATCH, a web-based math and problem-solving tutorial, in a traditionally arranged general chemistry classroom at the University of Kansas examined the impact of a designed intervention to assist students with the transfer of their mathematical knowledge to a chemistry context where it could be readily used for quantitative problem solving. The ReMATCH intervention, designed on constructivist-based pedagogies, focused on illuminating the expert-processes of problem solving and transferring knowledge across domains to the novice chemistry. The two implementations of ReMATCH -- once as lab assignments and once lecture assignments -- resulted in very different student responses to the intervention. However, within both, the beneficial effects of sustained ReMATCH-use were visible. In 2006, students who attempted all of the ReMATCH homework assignments were predicted to earn ˜5% higher on their total exam points. The 2007 implementation of ReMATCH demonstrated that students who attempted all of the homework problems and visited at least half of the ReMATCH tutorial pages were predicted to earn ˜8.5% higher on their total exam points. Additionally, use of ReMATCH in 2006 also resulted in increased confidence (as measured by comfort-level) with some of the math-related chemistry topics covered in ReMATCH. In 2007, when only students who attempted all of the ReMATCH problems were considered, it became clear that individuals who were initially less confident in their math-related chemistry skills were more likely to view more of the ReMATCH tutorial pages. When students with lower initial comfort-levels on these topics viewed at least half of the ReMATCH tutorial pages, they were able to compensate for their initially lower levels of confidence and were equally comfortable with most of the math-related chemistry topics by the final survey. Student interactions with and perceptions of ReMATCH showed that student attitudes towards Re

  6. A Coupled Chemistry-emission Model for Atomic Oxygen Green and Red-doublet Emissions in the Comet C/1996 B2 Hyakutake

    Science.gov (United States)

    Bhardwaj, Anil; Raghuram, Susarla

    2012-03-01

    The green (5577 Å) and red-doublet (6300, 6364 Å) lines are prompt emissions of metastable oxygen atoms in the 1 S and 1 D states, respectively, that have been observed in several comets. The value of the intensity ratio of green to red-doublet (G/R ratio) of 0.1 has been used as a benchmark to identify the parent molecule of oxygen lines as H2O. A coupled chemistry-emission model is developed to study the production and loss mechanisms of the O(1 S) and O(1 D) atoms and the generation of red and green lines in the coma of C/1996 B2 Hyakutake. The G/R ratio depends not only on photochemistry, but also on the projected area observed for cometary coma, which is a function of the dimension of the slit used and the geocentric distance of the comet. Calculations show that the contribution of photodissociation of H2O to the green (red) line emission is 30%-70% (60%-90%), while CO2 and CO are the next potential sources contributing 25%-50% (green lines and G/R ratios are in good agreement with the observations made on the comet Hyakutake in 1996 March.

  7. Coupled Chemistry-Emission Model for Atomic Oxygen Green and Red-doublet Emissions in Comet C/1996 B2 Hyakutake

    CERN Document Server

    Bhardwaj, Anil

    2012-01-01

    The green (5577 \\AA) and red-doublet (6300, 6364 \\AA) lines are prompt emissions of metastable oxygen atoms in the $^1$S and $^1$D states, respectively, that have been observed in several comets. The value of intensity ratio of green to red-doublet (G/R ratio) of 0.1 has been used as a benchmark to identify the parent molecule of oxygen lines as H$_2$O. A coupled chemistry-emission model is developed to study the production and loss mechanisms of O($^1$S) and O($^1$D) atoms and the generation of red and green lines in the coma of C/1996 B2 Hyakutake. The G/R ratio depends not only on photochemistry, but also on the projected area observed for cometary coma, which is a function of the dimension of the slit used and geocentric distance of the comet. Calculations show that the contribution of photodissociation of H$_2$O to the green (red) line emission is 30 to 70% (60 to 90%), while CO$_2$ and CO are the next potential sources contributing 25 to 50% ($<$5%). The ratio of the photo-production rate of O($^1$S)...

  8. Slow hydrogen atom transfer reactions of oxo- and hydroxo-vanadium compounds: the importance of intrinsic barriers.

    Science.gov (United States)

    Waidmann, Christopher R; Zhou, Xin; Tsai, Erin A; Kaminsky, Werner; Hrovat, David A; Borden, Weston Thatcher; Mayer, James M

    2009-04-08

    fluoride in place of the py ligands. The calculations reproduce the difference in barrier heights and show that transfer of a hydrogen atom involves more structural reorganization for vanadium than the Ru analogues. The vanadium complexes have larger changes in the metal-oxo and metal-hydroxo bond lengths, which is traced to the difference in d-orbital occupancy in the two systems. This study thus highlights the importance of intrinsic barriers in the transfer of a hydrogen atom, in addition to the thermochemical (bond strength) factors that have been previously emphasized.

  9. Combination of electrografting and atom-transfer radical polymerization for making the stainless steel surface antibacterial and protein antiadhesive.

    Science.gov (United States)

    Ignatova, Milena; Voccia, Samuel; Gilbert, Bernard; Markova, Nadya; Cossement, Damien; Gouttebaron, Rachel; Jérôme, Robert; Jérôme, Christine

    2006-01-03

    A two-step "grafting from" method has been successfully carried out, which is based on the electrografting of polyacrylate chains containing an initiator for the atom transfer radical polymerization (ATRP) of 2-(tert-butylamino)ethyl methacrylate (TBAEMA) or copolymerization of TBAEMA with either monomethyl ether of poly(ethylene oxide) methacrylate (PEOMA) or acrylic acid (AA) or styrene. The chemisorption of this type of polymer brushes onto stainless steel surfaces has potential in orthopaedic surgery. These films have been characterized by ATR-FTIR, Raman spectroscopy, atomic force microscopy (AFM), and measurement of contact angles of water. The polymer formed in solution by ATRP and that one detached on purpose from the surface have been analyzed by size exclusion chromathography (SEC) and (1)H NMR spectroscopy. The strong adherence of the films onto stainless steel has been assessed by peeling tests. AFM analysis has shown that addition of hydrophilic comonomers to the grafted chains decreases the surface roughness. According to dynamic quartz crystal microbalance experiments, proteins (e.g., fibrinogen) are more effectively repelled whenever copolymer brushes contain neutral hydrophilic (PEOMA) co-units rather than negatively charged groups (PAA salt). Moreover, a 2- to 3-fold decrease in the fibrinogen adsorption is observed when TBAEMA is copolymerized with either PEOMA or AA rather than homopolymerized or copolymerized with styrene. Compared to the bare stainless steel surface, brushes of polyTBAEMA, poly(TBAEMA-co-PEOMA) and poly(TBAEMA-co-AA) decrease the bacteria adhesion by 3 to 4 orders of magnitude as revealed by Gram-positive bacteria S. aureus adhesion tests.

  10. Surface Chemistry and Interface Evolution during the Atomic Layer Deposition of High-k Metal Oxides on InAs(100) and GaAs(100) Surfaces

    Science.gov (United States)

    Henegar, Alex J.

    Device scaling has been key for creating faster and more powerful electronic devices. Integral circuit components like the metal-oxide semiconductor field-effect transistor (MOSFET) now rely on material deposition techniques, like atomic layer deposition (ALD), that possess atomic-scale thickness precision. At the heart of the archetypal MOSFET is a SiO2/Si interface which can be formed to near perfection. However when the thickness of the SiO 2 layer is shrunk down to a few nanometers several complications arise like unacceptably high leakage current and power consumption. Replacing Si with III-V semiconductors and SiO2 with high-k dielectric materials is appealing but comes with its own set of challenges. While SiO2 is practically defect-free, the native oxides of III-Vs are poor dielectrics. In this dissertation, the surface chemistry and interface evolution during the ALD of high-k metal oxides on Si(100), GaAs(100) and InAs(100) was studied. In particular, the surface chemistry and crystallization of TiO2 films grown on Si(100) was investigated using transmission Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). Large, stable, and highly reactive anatase TiO2 grains were found to form during a post-deposition heat treatment after the ALD at 100 °C. The remainder of this work was focused on the evolution of the interfacial oxides during the deposition of TiO2 and Al2O3 on InAs(100) and GaAs(100) and during the deposition of Ta2O 5 on InAs(100). In summary the ALD precursor type, deposited film, and substrate had an influence in the evolution of the native oxides. Alkyl amine precursors fared better at removing the native oxides but the deposited films (TiO2 and Ta2O5) were susceptible to significant native oxide diffusion. The alkyl precursor used for the growth of Al 2O3 was relatively ineffective at removing the oxides but was

  11. Hydrophilic Modification of Microporous Polysulfone Membrane via Surface-Initiated Atom Transfer Radical Polymerization and Hydrolysis of Poly(glycidylmethacrylate)%Hydrophilic Modification of Microporous Polysulfone Membrane via Surface-Initiated Atom Transfer Radical Polymerization and Hydrolysis of Poly(glycidylmethacrylate)

    Institute of Scientific and Technical Information of China (English)

    王超展; 赵飒; 卫引茂

    2012-01-01

    Poly(glycidylmethacrylate) (PGMA) brushes were grafted from chloromethylated polysulfone (CMPSF) mem- brane surface by surface-initiated atom transfer radical polymerization (S1-ATRP), and the grafting was followed by hydrolysis of epoxy groups in the grafting chains to improve the membrane's hydrophilie property. Fourier trans- form infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) measurements confirmed the suc- cessful grafting and hydrolysis of PGMA. The grafting degree of the monomer, measured by periodic acid titration and gravimetric analysis, increased linearly with the polymerization time, while the static water contact angle of the membrane grafted with PGMA or hydrolyzed PGMA linearly decreased. In comparison with the PGMA-grafted membranes, the hydrolyzed PGMA-grafted membranes possess stronger hydrophilicity as indicated by their contact angle and hydration capacity, and as a result they have an improved antifouling property. Therefore, the control of the hydrophilicity of PSF membrane could be realized through adjusting the polymerization time and transforming the functional groups in the grafting chain.

  12. Atomic Scale Imaging of the Electronic Structure and Chemistry of Graphene and Its Precursors on Metal Surfaces

    Energy Technology Data Exchange (ETDEWEB)

    Flynn, George W. [Columbia Univ., New York, NY (United States)

    2015-02-16

    The objectives of this project were to reveal the mechanisms and reaction processes that solid carbon materials undergo when combining with gases such as oxygen, water vapor and hydrocarbons. This research was focused on fundamental chemical events taking place on single carbon sheets of graphene, a two-dimensional, polycyclic carbon material that possesses remarkable chemical and electronic properties. Ultimately, this work is related to the role of these materials in mediating the formation of polycyclic aromatic hydrocarbons (PAH’s), their reactions at interfaces, and the growth of soot particles. Our intent has been to contribute to a fundamental understanding of carbon chemistry and the mechanisms that control the formation of PAH’s, which eventually lead to the growth of undesirable particulates. We expect increased understanding of these basic chemical mechanisms to spur development of techniques for more efficient combustion of fossil fuels and to lead to a concomitant reduction in the production of undesirable solid carbon material.

  13. Surface modification of glycidyl-containing poly(methyl methacrylate) microchips using surface-initiated atom-transfer radical polymerization.

    Science.gov (United States)

    Sun, Xuefei; Liu, Jikun; Lee, Milton L

    2008-02-01

    Fabrication of microfluidic systems from polymeric materials is attractive because of simplicity and low cost. Unfortunately, the surfaces of many polymeric materials can adsorb biological samples. Therefore, it is necessary to modify their surfaces before these polymeric materials can be used for separation and analysis. Oftentimes it is difficult to modify polymeric surfaces because of their resistance to chemical reaction. Recently, we introduced a surface-reactive acrylic polymer, poly(glycidyl methacrylate-co-methyl methacrylate) (PGMAMMA), which can be modified easily and is suitable for fabrication of microfluidic devices. Epoxy groups on the surface can be activated by air plasma treatment, hydrolysis, or aminolysis. In this work, the resulting hydroxyl or amino groups were reacted with 2-bromoisobutylryl bromide to introduce an initiator for surface-initiated atom-transfer radical polymerization (SI-ATRP). Polyethylene glycol (PEG) layers grown on the surface using this method were uniform, hydrophilic, stable, and resistant to protein adsorption. Contact angle measurement and X-ray photoelectron spectroscopy (XPS) were used to characterize activated polymer surfaces, initiator-bound surfaces, and PEG-grafted surfaces. We obtained excellent capillary electrophoresis (CE) separations of proteins and peptides with the PEG-modified microchips. A separation efficiency of 4.4 x 10(4) plates for a 3.5 cm long separation channel was obtained.

  14. Conventional and atom transfer radical copolymerization of phenoxycarbonylmethyl methacrylate-styrene and thermal behavior of their copolymers

    Directory of Open Access Journals (Sweden)

    2007-08-01

    Full Text Available The atom transfer radical polymerization (ATRP of phenoxycarbonylmethyl methacrylate (PCMMA with styrene (St were performed in bulk at 110°C in the presence of ethyl 2-bromoacetate, cuprous(Ibromide (CuBr, and N,N,N’,N”,N”-pentamethyldiethyltriamine. Also, a series conventional free-radical polymerization (CFRP of PCMMA and styrene were carried out in the presence of 2,2’-azobisisobutyronitrile in 1,4-dioxane solvent at 60°C. The structure of homo and copolymers was characterized by IR, 1H and 13C-NMR techniques. The composition of the copolymers was calculated by 1H-NMR spectra. The average-molecular weight of the copolymers were investigated by Gel Permeation Chromatography (GPC. For copolymerization system, their monomer reactivity ratios were obtained by using both Kelen-Tüdõs and Fineman-Ross equations. Thermal analysis measurements of homo- and copolymers prepared CFRP and ATRP methods were measured by TGA-50 and DSC-50. Blends of poly(PCMMA and poly(St obtained via ATRP method have been prepared by casting films from dichlorormethane solution. The blends were characterized by differential scanning calorimetry. The initial decomposition temperatures of the resulting copolymers increased with increasing mole fraction of St.

  15. Ph(i-PrO)SiH2: An Exceptional Reductant for Metal-Catalyzed Hydrogen Atom Transfers.

    Science.gov (United States)

    Obradors, Carla; Martinez, Ruben M; Shenvi, Ryan A

    2016-04-13

    We report the discovery of an outstanding reductant for metal-catalyzed radical hydrofunctionalization reactions. Observations of unexpected silane solvolysis distributions in the HAT-initiated hydrogenation of alkenes reveal that phenylsilane is not the kinetically preferred reductant in many of these transformations. Instead, isopropoxy(phenyl)silane forms under the reaction conditions, suggesting that alcohols function as important silane ligands to promote the formation of metal hydrides. Study of its reactivity showed that isopropoxy(phenyl)silane is an exceptionally efficient stoichiometric reductant, and it is now possible to significantly decrease catalyst loadings, lower reaction temperatures, broaden functional group tolerance, and use diverse, aprotic solvents in iron- and manganese-catalyzed hydrofunctionalizations. As representative examples, we have improved the yields and rates of alkene reduction, hydration, hydroamination, and conjugate addition. Discovery of this broadly applicable, chemoselective, and solvent-versatile reagent should allow an easier interface with existing radical reactions. Finally, isotope-labeling experiments rule out the alternative hypothesis of hydrogen atom transfer from a redox-active β-diketonate ligand in the HAT step. Instead, initial HAT from a metal hydride to directly generate a carbon-centered radical appears to be the most reasonable hypothesis.

  16. Rational preparation of dibenzothiophene-imprinted polymers by surface imprinting technique combined with atom transfer radical polymerization

    Science.gov (United States)

    Yang, Wenming; Liu, Lukuan; Zhou, Zhiping; Liu, Hong; Xie, Binze; Xu, Wanzhen

    2013-10-01

    A computational simulation method is introduced to simulate the dibenzothiophene-monomer pre-assembly system of molecular imprinted polymers. The interaction type and intensity between dibenzothiophene and monomer are discussed from the binding energy and spatial position distribution. The simulation and analysis results indicate that the amount of the function monomer is not the more the better in preparing molecular imprinted polymers. Based on the above results, a novel dibenzothiophene-imprinted polymers with the favorable specific adsorption effect was prepared by surface imprinting technique combined with atom transfer radical polymerization. This combined technologies are used for preparing a desulfurization adsorbent for the first time. Various measures were selected to characterize the structure and morphology of the prepared adsorbent. The characterization results show that the adsorbent has suitable features for further adsorption process. A series of static adsorption experiments were conducted to analyze its adsorption performance. The adsorption process follows Elovich model by the kinetic analysis and Sips equation by the isothermal analysis. The approach we described will provide another opportunity in the deep desulfurization field.

  17. Effect of Trapping Agent and Polystyrene Chain End Functionality on Radical Trap-Assisted Atom Transfer Radical Coupling

    Directory of Open Access Journals (Sweden)

    Elizabeth M. Carnicom

    2014-10-01

    Full Text Available Coupling reactions were performed to gauge the effect of the inclusion of a radical trap on the success of coupling reactions of monohalogenated polystyrene (PSX chains in atom transfer radical coupling (ATRC type reactions. The effect of both the specific radical trap chosen and the structure of the polymer chain end were evaluated by the extent of dimerization observed in a series of analogous coupling reactions. The commonly used radical trap 2-methyl-2-nitrosopropane (MNP showed the highest amounts of dimerization for PSX (X = Br, Cl compared to coupling reactions performed in its absence or with a different radical trap. A dinitroxide coupling agent was also studied with the extent of coupling nearly matching the effectiveness of MNP in RTA (Radical trap-assisted-ATRC reactions, while N-nitroso and electron rich nitroso coupling agents were the least effective. (2,2,6,6-Tetramethyl-piperin-l-yloxyl-capped PS (PS-TEMPO, prepared by NMP, was subjected to a coupling sequence conceptually similar to RTA-ATRC, but dimerization was not observed regardless of the choice of radical trap. Kinetic experiments were performed to observe rate changes on the coupling reaction of PSBr as a result of the inclusion of MNP, with substantial rate enhancements found in the RTA-ATRC coupling sequence compared to traditional ATRC.

  18. Grafting of thermoresponsive polymer from the surface of functionalized multiwalled carbon nanotubes via atom transfer radical polymerization

    Institute of Scientific and Technical Information of China (English)

    XU GuoYong; XIA Ru; WANG Hu; MENG XiangChun; ZHU QingRen

    2008-01-01

    Multiwalled carbon nanotubes were oxidized with concentrated HNOz and H2SO4 to introduce carboxylic groups onto carbon nanotubes surfaces. The oxidized carbon nanotubes were reacted subsequently with thionyl chloride and 2-Hydroxylethyl-2'-bromoisobutyrate, producing MWNT-based macroinitiators, MWNT-Br, for the atom transfer radical polymerization of (N-isopropylacrylamide). FTIR, XPS, 1H NMR, Raman and TGA were used to characterize the resulting products and to determine the content of the water-soluble poly (N-isopropylacrylamide) chains in the product. The MWNTs grafted with PNIPAM chains have good solubility in distilled water; THF and CHCl3. TEM images of the samples provide direct evidence for the formation of a nanostructure that MWNTs coated with polymer layer. The produced MWNT-g-PNIPAM has a PNIPAM shell, which is very sensitive to the change of temperature.This method would open a door for the fabrication of novel functional carbon nanotube-based nanomaterials or nanodevices with designable structure and tailor-made properties.

  19. Absolute rate constants for hydrogen atom transfer from tertiary amides to the cumyloxyl radical: evaluating the role of stereoelectronic effects.

    Science.gov (United States)

    Salamone, Michela; Milan, Michela; DiLabio, Gino A; Bietti, Massimo

    2014-08-01

    A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from a series of alkanamides to the cumyloxyl radical (CumO(•)) was carried out. With N,N-dialkylformamides HAT preferentially occurs from the formyl C-H bond, while in N-formylpyrrolidine HAT mostly occurs from the ring α-C-H bonds. With the acetamides and the alkanamides almost exclusive HAT from the C-H bonds that are α to nitrogen was observed. The results obtained show that alignment between the C-H bond being broken and the amide π-system can lead to significant increases in the HAT rate constant (kH). This finding points toward the important role of stereoelectronic effects on the HAT reactivity and selectivity. The highest kH values were measured for the reactions of CumO(•) with N-acylpyrrolidines. These substrates have ring α-C-H bonds that are held in a conformation that is optimally aligned with the amide π-system, thus allowing for the relatively facile HAT reaction. The lowest kH value was measured for the reaction of N,N-diisobutylacetamide, wherein the steric bulk associated with the N-isobutyl groups increases the energy barrier required to reach the most suitable conformation for HAT. The experimental results are well supported by the computed BDEs for the C-H bonds of the most representative substrates.

  20. Lipase Immobilization onto the Surface of PGMA-b-PDMAEMA-grafted Magnetic Nanoparticles Prepared via Atom Transfer Radical Polymerization☆

    Institute of Scientific and Technical Information of China (English)

    Jingyun Wang; Fangling Ji; Jishuang Xing; Shuang Cui; Yongming Bao; Wenbo Hao

    2014-01-01

    A block copolymer of 2-dimethylaminoethyl methacrylate (DMAEMA) and glycidyl methacrylate (GMA) was grafted onto the surface of magnetic nanoparticles (Fe3O4) via atom transfer radical polymerization. The resultant PGMA-b-PDMAEMA-grafted-Fe3O4 magnetic nanoparticles with amino and epoxy groups were characterized by Fourier transform infrared spectroscopy, powder X-ray diffraction, thermo-gravimetric analysis, and scanning electron microscopy. Lipase from Burkholderia cepacia was successfully immobilized onto the magnetic nanoparticles by physical adsorption and covalent bonding. The immobilization capacity of the magnetic particles is 0.5 mg lipase per mg support, with an activity recovery of up to 43.1%under the optimum immobilization condition. Biochemical characterization shows that the immobilized lipase exhibits improved thermal stability, good tolerance to organic solvents with high lg P, and higher pH stability than the free lipase at pH 9.0. After six consecutive cycles, the residual activity of the immobilized lipase is still over 55%of its initial activity.

  1. 3D scaffolds from vertically aligned carbon nanotubes/poly(methyl methacrylate) composites via atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Tebikachew, Behabtu; Magina, Sandra [CICECO, Department of Chemistry, University of Aveiro (Portugal); Mata, Diogo; Oliveira, Filipe J.; Silva, Rui F. [CICECO, Department of Materials and Ceramic Engineering, University of Aveiro (Portugal); Barros-Timmons, Ana, E-mail: anabarros@ua.pt [CICECO, Department of Chemistry, University of Aveiro (Portugal)

    2015-01-15

    Vertically aligned carbon nanotubes (VACNTs) synthesized by Thermal Chemical Vapour Deposition (TCVD) were modified using an Ar:O{sub 2} (97:3) plasma to generate oxygen-containing functional groups on the surface for subsequent modification. X-ray photo-emission spectroscopy (XPS) and micro-Raman analyses confirmed the grafting of those functional groups onto the surface of the nanotubes as well as the removal of amorphous carbon produced and deposited on the VACNT forests during the CVD process. The plasma treated VACNT forests were further modified with 2-bromo-2-methylpropionyl bromide, an atom transfer radical polymerization (ATRP) initiator, to grow poly(methyl methacrylate) (PMMA) chains from the forests via ATRP. Scanning transmission electron microscopy (STEM) of the ensuing VACNT/PMMA composites confirmed the coating of the nanotube forests with the PMMA polymer. 3D scaffolds of polymeric composites with honeycomb like structure were then obtained. Compressive tests have shown that the VACNT/PMMA composite has higher compressive strength than the pristine forest. - Highlights: • Vertically aligned carbon nanotubes (VACNTs) were synthesized and plasma modified. • X-ray photo-emission and Raman spectroscopies confirmed the VACNTs modification. • Poly(methyl methacrylate) chains were grown via ATRP from the VACNTs. • STEM of the VACNT/PMMA composites confirmed that PMMA surrounds the nanotubes. • VACNT/PMMA composite has higher compressive strength compared to the pristine forest.

  2. Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

    Science.gov (United States)

    Yuan, Huihui; Qian, Bin; Zhang, Wei; Lan, Minbo

    2016-02-01

    An anti-fouling surface of polyurethane (PU) film grafted with Poly(N-vinylpyrrolidone) (PVP) was prepared through surface-initiated atom transfer radical polymerization (SI-ATRP). And the polymerization time was investigated to obtain PU films with PVP brushes of different lengths. The surface properties and protein adsorption of modified PU films were evaluated. The results showed that the hydrophilicity of PU-PVP films were improved with the increase of polymerization time, which was not positive correlation with the surface roughness due to the brush structure. Additionally, the protein resistance performance was promoted when prolonging the polymerization time. The best antifouling PU-PVP (6.0 h) film reduced the adsoption level of bovine serum albumin (BSA), lysozyme (LYS), and brovin serum fibrinogen (BFG) by 93.4%, 68.3%, 85.6%, respectively, compared to the unmodified PU film. The competitive adsorption of three proteins indicated that LYS preferentially adsorbed on the modified PU film, while BFG had the lowest adsorption selectivity. And the amount of BFG on PU-PVP (6.0 h) film reduced greatly to 0.08 μg/cm2, which was almost one-tenth of its adsorption from the single-protein system. Presented results suggested that both hydrophilicity and surface roughness might be the important factors in all cases of protein adsorption, and the competitive or selective adsorption might be related to the size of the proteins, especially on the non-charged films.

  3. Photodissociation of pyrrole-ammonia clusters by velocity map imaging: mechanism for the H-atom transfer reaction.

    Science.gov (United States)

    Rubio-Lago, L; Amaral, G A; Oldani, A N; Rodríguez, J D; González, M G; Pino, G A; Bañares, L

    2011-01-21

    The photodissociation dynamics of pyrrole-ammonia clusters (PyH·(NH(3))(n), n = 2-6) has been studied using a combination of velocity map imaging and non-resonant detection of the NH(4)(NH(3))(n-1) products. The excited state hydrogen-atom transfer mechanism (ESHT) is evidenced through delayed ionization and presents a threshold around 236.6 nm, in agreement with previous reports. A high resolution determination of the kinetic energy distributions (KEDs) of the products reveals slow (∼0.15 eV) and structured distributions for all the ammonia cluster masses studied. The low values of the measured kinetic energy rule out the existence of a long-lived intermediate state, as it has been proposed previously. Instead, a direct N-H bond rupture, in the fashion of the photodissociation of bare pyrrole, is proposed. This assumption is supported by a careful analysis of the structure of the measured KEDs in terms of a discrete vibrational activity of the pyrrolyl co-fragment.

  4. Thermoresponsive Melamine Sponges with Switchable Wettability by Interface-Initiated Atom Transfer Radical Polymerization for Oil/Water Separation.

    Science.gov (United States)

    Lei, Zhiwen; Zhang, Guangzhao; Deng, Yonghong; Wang, Chaoyang

    2017-03-15

    Here we have obtained a temperature responsive melamine sponge with a controllable wettability between superhydrophilicity and superhydrophobicity by grafting the octadecyltrichlorosilane and thermoresponsive poly(N-isopropylacrylamide) (PNIPAAm) onto the surface of melamine sponge skeletons. The whole process included the silanization in which step the rough surface with low surface energy and the NH2 were provided, and the atom transfer radical polymerization which ensured the successful grafting of PNIPAAm onto the skeleton's surface. The product exhibits a good reversible switch between superhydrophilicity and superhydrophobicity by changing the temperature below or above the lower critical solution temperature (LCST, about 32 °C) of PNIPAAm, and the modified sponge still retains a good responsiveness after undergoing two temperature switches for 20 cycles. Simultaneously, the functionalized sponges could be used to absorb the oil under water at 37 °C, and they released the absorbed oil in various ways under water at 20 °C, showing wide potential applications including oil/water separation.

  5. Facile synthesis of thermally stable poly(N-vinylpyrrolidone)-modified gold surfaces by surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Liu, Xiaoli; Sun, Kai; Wu, Zhaoqiang; Lu, Jianhong; Song, Bo; Tong, Weifang; Shi, Xiujuan; Chen, Hong

    2012-06-26

    Well-controlled polymerization of N-vinylpyrrolidone (NVP) on Au surfaces by surface-initiated atom transfer radical polymerization (SI-ATRP) was carried out at room temperature by a silanization method. Initial attempts to graft poly(N-vinylpyrrolidone) (PVP) layers from initiators attached to alkanethiol monolayers yielded PVP films with thicknesses less than 5 nm. The combined factors of the difficulty in the controllable polymerization of NVP and the instability of alkanethiol monolayers led to the difficulty in the controlled polymerization of NVP on Au surfaces. Therefore, the silanization method was employed to form an adhesion layer for initiator attachment. This method allowed well-defined ATRP polymerization to occur on Au surfaces. Water contact angle, X-ray photoelectron spectroscopy (XPS), and reflectance Fourier transform infrared (reflectance FTIR) spectroscopy were used to characterize the modified surfaces. The PVP-modified gold surface remained stable at 130 °C for 3 h, showing excellent thermal stability. Thus, postfunctionalization of polymer brushes at elevated temperatures is made possible. The silanization method was also applied to modify SPR chips and showed potential applications in biosensors and biochips.

  6. Effect of Surface Charge on Surface-Initiated Atom Transfer Radical Polymerization from Cellulose Nanocrystals in Aqueous Media.

    Science.gov (United States)

    Zoppe, Justin O; Xu, Xingyu; Känel, Cindy; Orsolini, Paola; Siqueira, Gilberto; Tingaut, Philippe; Zimmermann, Tanja; Klok, Harm-Anton

    2016-04-11

    Cellulose nanocrystals (CNCs) with different charge densities were utilized to examine the role of electrostatic interactions on surface-initiated atom transfer radical polymerization (SI-ATRP) in aqueous media. To this end, growth of hydrophilic uncharged poly(N,N-dimethylacrylamide) (PDMAM) brushes was monitored by electrophoresis, (1)H NMR spectroscopy, and dynamic light scattering (DLS). Molecular weight and polydispersity of PDMAM brushes was determined by GPC analysis of hydrolytically cleaved polymers. Initiator and polymer brush grafting densities, and thus, initiator efficiencies were derived from elemental analysis. Higher initiator efficiency of polymer brush growth was observed for CNCs with higher anionic surface sulfate half-ester group density, but at the expense of high polydispersity caused by inefficient deactivation. PDMAM grafts with number-average molecular weights up to 530 kDa and polydispersity indices interfacial region at the onset of polymerization is proposed. The results presented here could have implications for other substrates that present surface charges and for the assumption that the kinetics of Cu-mediated SI-CRP are analogous to those conducted in solution.

  7. Energy transfer among distant quantum systems in spatially shaped laser fields: Two H atoms with the internuclear separation of 5.29 nm (100 a.u.)

    CERN Document Server

    Paramonov, Guennaddi K; Bandrauk, Andre D

    2010-01-01

    The quantum dynamics of two distant H atoms excited by ultrashort and spatially shaped laser pulses is studied by the numerical solution of the non-Born-Oppenheimer time-dependent Schr\\"odinger equation within a three-dimensional (3D) model, including the internuclear distance R and the two z coordinates of the electrons, z1 and z2. The two 1D hydrogen atoms, A and B, are assumed to be initially in their ground states with a large (but otherwise arbitrary) internuclear separation of R = 100 a.u. (5.29 nm). Two types of a spatial envelope of a laser field linearly po- larized along the z-axis are considered: (i) a broad Gaussian envelope, such that atom A is excited by the laser field predominantly, and (ii) a narrow envelope, such that practically only atom A is excited by the laser field. With the laser carrier frequency {\\omega} = 1.0 a.u. and the pulse duration tp = 5 fs, in both cases an efficient energy transfer from atom A to atom B has been found. The ionization of atom B achieved mostly after the end ...

  8. Chemistry of recoil atoms of bromine-82 in neutron-irradiated crystalline perbromates of the alkali metals and ammonium

    Energy Technology Data Exchange (ETDEWEB)

    Gavrilov, V.V.; Isupov, V.K.; Kirin, I.S.

    1975-01-01

    It was established by ion exchange chromatography that the recoil atoms of bromine-82 in perbromates with thermal neutrons are stabilized in the form of five valence forms: BrO/sub 4//sup -/, BrO/sub 3//sup -/, BrO/sub 2//sup -/, BrO/sup -/, Br/sup -/. The retention of bromine-82 of BrO/sub 4//sup -/ is 2.1 +- 0.4 percent for LiBrO/sub 4/, 2.1 +- 0.4 percent for NaBrO/sub 4/, 2.3 +- 0.4 percent for KBrO/sub 4/, 2.6 +- 0.4 percent for RbBrO/sub 4/, 2.2 +- 0.4 percent for CsBrO/sub 4/, and 1.6 +- 0.4 percent for NH/sub 4/BrO/sub 4/.

  9. Unification of anion relay chemistry with the Takeda and Hiyama cross-coupling reactions: identification of an effective silicon-based transfer agent.

    Science.gov (United States)

    Smith, Amos B; Hoye, Adam T; Martinez-Solorio, Dionicio; Kim, Won-Suk; Tong, Rongbiao

    2012-03-14

    The unification of Anion Relay Chemistry (ARC) with the Takeda and Hiyama palladium-mediated cross-coupling processes to provide aryl-aryl, alkenyl-aryl, and alkenyl-alkenyl coupled products by exploiting a common silicon-based transfer agent has been achieved. These results provide a practical solution for intermolecular cross-coupling of organolithium reagents without the problematic lithium-halogen exchange and/or undesired homocoupling that has kept organolithium cross-couplings from achieving the same level of utility asother palladium-mediated methods (e.g., Suzuki organoboron, Negishi organozinc, Stille organotin, Kumada organomagnesium, etc.).

  10. Additive effects in halogen hot atom chemistry. I. Nuclear reaction (. gamma. ,n) in bromobenzene, fluorobenzene-amine systems

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Y.; Fu, K.; Li, W.; Wang, T.

    1980-05-01

    (1) For observing the chemical effects of the nuclear reaction /sup 79/Br(..gamma..,n)/sup 78/Br in liquid bromobenzene, the nitrogen-containing compounds, such as aniline, diphenylamine, phenylhydrazine and pyridine, were used as additives respectively during irradiation. Similarly, aniline, diphenylamine, phenylhydrazine, dimethylaniline and pyridine were added in liquid fluorobenzene when the reaction /sup 19/F(..gamma..,n)/sup 18/F proceeded. The curves indicating the dependence of recoil atom retention to the additive mole concentration were plotted, and each curve typically showed the general characteristics of dropping sharply in low mol % of additive and gradually in high mol %. (2) The relative effectiveness of additives in depressing organic retention was revealed in the following order: phenylhydrazine > aniline greater than or equal to dimethylaniline > diphenylamine greater than or equal to pyridine. In our opinion the reactivity of nitrogen lone-pair electrons, which is influenced and bounded by the Pi-bond delocalization of the aromatic amine molecule, substantially determines this effectiveness order. (3) Adding the inert additive benzene or toluene to the fluorobenzene system, a linear dependence of retention to additive concentration was obtained. The contribution of the reactive functional group NHNH/sub 2/ of phenylhydrazine in reducing the retention chemically could be evaluated by the comparison of the benzene line with the phenylhydrazine curve.

  11. A COUPLED CHEMISTRY-EMISSION MODEL FOR ATOMIC OXYGEN GREEN AND RED-DOUBLET EMISSIONS IN THE COMET C/1996 B2 HYAKUTAKE

    Energy Technology Data Exchange (ETDEWEB)

    Bhardwaj, Anil; Raghuram, Susarla, E-mail: bhardwaj_spl@yahoo.com, E-mail: anil_bhardwaj@vssc.gov.in, E-mail: raghuramsusarla@gmail.com [Space Physics Laboratory, Vikram Sarabhai Space Centre, Trivandrum 695022 (India)

    2012-03-20

    The green (5577 Angstrom-Sign ) and red-doublet (6300, 6364 Angstrom-Sign ) lines are prompt emissions of metastable oxygen atoms in the {sup 1}S and {sup 1}D states, respectively, that have been observed in several comets. The value of the intensity ratio of green to red-doublet (G/R ratio) of 0.1 has been used as a benchmark to identify the parent molecule of oxygen lines as H{sub 2}O. A coupled chemistry-emission model is developed to study the production and loss mechanisms of the O({sup 1}S) and O({sup 1}D) atoms and the generation of red and green lines in the coma of C/1996 B2 Hyakutake. The G/R ratio depends not only on photochemistry, but also on the projected area observed for cometary coma, which is a function of the dimension of the slit used and the geocentric distance of the comet. Calculations show that the contribution of photodissociation of H{sub 2}O to the green (red) line emission is 30%-70% (60%-90%), while CO{sub 2} and CO are the next potential sources contributing 25%-50% (<5%). The ratio of the photoproduction rate of O({sup 1} S) to O({sup 1} D) would be around 0.03 ({+-}0.01) if H{sub 2}O is the main source of oxygen lines, whereas it is {approx}0.6 if the parent is CO{sub 2}. Our calculations suggest that the yield of O({sup 1} S) production in the photodissociation of H{sub 2}O cannot be larger than 1%. The model-calculated radial brightness profiles of the red and green lines and G/R ratios are in good agreement with the observations made on the comet Hyakutake in 1996 March.

  12. Multiple Electron Charge Transfer Chemistries for Electrochemical Energy Storage Systems: The Metal Boride and Metal Air Battery

    Science.gov (United States)

    Stuart, Jessica F.

    (g) → CO 32- (molten) (2a) CO32- (molten) ?→ C (solid) + O2 (g) + O2- (dissolved) (2b). Thus, powered by the oxidation of carbon formed directly from the CO 2 in our earth's atmosphere, the carbon molten air battery is a viable system to provide large-scale energy storage. These batteries are rechargeable and have amongst the highest intrinsic battery storage capacities available. The electron charge transfer chemistry is demonstrated through three examples. These examples utilize iron, carbon, and vanadium diboride as reactive materials, each containing intrinsic volumetric energy capacities of 10,000 Wh/L for Fe to Fe (III), 19,000 Wh/L for C to CO2, and 27,000 Wh/L for VB2 to B2O3 and V2O 5, compared to 6,200 Wh/L for the lithium air battery.

  13. Direct detection by atomic force microscopy of single bond forces associated with the rupture of discrete charge-transfer complexes.

    Science.gov (United States)

    Skulason, Hjalti; Frisbie, C Daniel

    2002-12-18

    Atomic force microscopy (AFM) was used to measure the chemical binding force of discrete electron donor-acceptor complexes formed at the interface between proximal self-assembled monolayers (SAMs). Derivatives of the well-known electron donor N,N,N',N'-tetramethylphenylenediamine (TMPD) and the electron acceptor 7,7,8,8-tetracyanoquinodimethane (TCNQ) were immobilized on Au-coated AFM tips and substrates by formation of SAMs of N,N,N'-trimethyl-N'-(10-thiodecyl)-1,4-phenylenediamine (I) and bis(10-(2-((2,5-cyclohexadiene-1,4-diylidene)dimalonitrile))decyl) disulfide (II), respectively. Pull-off forces between modified tips and substrates were measured under CHCl(3) solvent. The mean pull-off forces associated with TMPD/TCNQ microcontacts were more than an order of magnitude larger than the pull-off forces for TMPD/TMPD and TCNQ/TCNQ microcontacts, consistent with the presence of specific charge-transfer interactions between proximal TMPD donors and TCNQ acceptors. Furthermore, histograms of pull-off forces for TMPD/TCNQ contacts displayed 70 +/- 15 pN periodicity, assigned to the rupture of individual TMPD-TCNQ donor-acceptor (charge-transfer) complexes. Both the mean pull-off force and the 70 pN force quantum compare favorably with a contact mechanics model that incorporates the effects of discrete chemical bonds, solvent surface tensions, and random contact area variations in consecutive pull-offs. From the 70 pN force quantum, we estimate the single bond energy to be approximately 4-5 kJ/mol, in reasonable agreement with thermodynamic data. These experiments establish that binding forces due to discrete chemical bonds can be detected directly in AFM pull-off measurements employing SAM modified probes and substrates. Because SAMs can be prepared with a wide range of exposed functional groups, pull-off measurements between SAM-coated tips and substrates may provide a general strategy for directly measuring binding forces associated with a variety of simple

  14. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts: A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis; James A. Dumesic; Amit A. Gokhale; Rahul P. Nabar; Calvin H. Bartholomew; Hu Zou; Brian Critchfield

    2006-03-03

    Efforts during this second year focused on four areas: (1) continued searching and summarizing of published Fischer-Tropsch synthesis (FTS) mechanistic and kinetic studies of FTS reactions on iron catalysts; (2) investigation of CO adsorption/desorption and temperature programmed hydrogenation (TPH) of carbonaceous species after FTS on unsupported iron and alumina-supported iron catalysts; (3) activity tests of alumina-supported iron catalysts in a fixed bed reactor; (4) sequential design of experiments, for the collection of rate data in a Berty CSTR reactor, and nonlinear-regression analysis to obtain kinetic parameters. Literature sources describing mechanistic and kinetic studies of Fischer-Tropsch synthesis on iron catalysts were compiled in a review. Temperature-programmed desorption/reaction methods (the latter using mass-spectrometry detection and also thermogravimetric analyzer (TGA)) were utilized to study CO adsorption/-desorption on supported and unsupported iron catalysts. Molecular and dissociative adsorptions of CO occur on iron catalysts at 25-150 C. The amounts adsorbed and bond strengths of adsorption are influenced by supports and promoters. That CO adsorbs dissociatively on polycrystalline Fe at temperatures well below those of FT reaction indicates that CO dissociation is facile and unlikely to be the rate-limiting step during FTS. Carbonaceous species formed after FT reaction for only 5 minutes at 200 C were initially hydrogenated under mild, isothermal condition (200 C and 1 atm), followed by TPH to 800 C. During the mild, isothermal hydrogenation, only about 0.1-0.2 mL of atomic carbon is apparently removed, while during TPH to 800 C multilayer equivalents of atomic, polymeric, carbidic, and graphitic carbons are removed. Rates of CO conversion on alumina-supported iron catalysts at 220-260 C and 20 atm are correlated well by a Langmuir-Hinshelwood expression, derived assuming carbon hydrogenation to CH and OH recombination to water to be

  15. Surface chemistry of group 11 atomic layer deposition precursors on silica using solid-state nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Pallister, Peter J.; Barry, Seán T.

    2017-02-01

    The use of chemical vapour deposition (CVD) and atomic layer deposition (ALD) as thin film deposition techniques has had a major impact on a number of fields. The deposition of pure, uniform, conformal thin films requires very specific vapour-solid reactivity that is largely unknown for the majority of ALD and CVD precursors. This work examines the initial chemisorption of several thin film vapour deposition precursors on high surface area silica (HSAS) using 13C, 31P, and quantitative 29Si nuclear magnetic resonance spectroscopy (NMR). Two copper metal precursors, 1,3-diisopropyl-imidazolin-2-ylidene copper (I) hexamethyldisilazide (1) and 1,3-diethyl-imidazolin-2-ylidene copper(I) hexamethyldisilazide (2), and one gold metal precursor, trimethylphosphine gold(III) trimethyl (3), are examined. Compounds 1 and 2 were found to chemisorb at the hydroxyl surface-reactive sites to form a ||-O-Cu-NHC surface species and fully methylated silicon (||-SiMe3, due to reactivity of the hexamethyldisilazane (HMDS) ligand on the precursor) at 150 °C and 250 °C. From quantitative 29Si solid-state NMR (SS-NMR) spectroscopy measurements, it was found that HMDS preferentially reacts at geminal disilanol surface sites while the copper surface species preferentially chemisorbed to lone silanol surface species. Additionally, the overall coverage was strongly dependent on temperature, with higher overall coverage of 1 at higher temperature but lower overall coverage of 2 at higher temperature. The chemisorption of 3 was found to produce a number of interesting surface species on HSAS. Gold(III) trimethylphosphine, reduced gold phosphine, methylated phosphoxides, and graphitic carbon were all observed as surface species. The overall coverage of 3 on HSAS was only about 10% at 100 °C and, like the copper compounds, had a preference for lone silanol surface reactive sites. The overall coverage and chemisorbed surface species have implications to the overall growth rate and purity of

  16. Protein adsorption resistance of PVP-modified polyurethane film prepared by surface-initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Yuan, Huihui; Qian, Bin; Zhang, Wei [Shanghai Key Laboratory of Functional Materials Chemistry and Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); Lan, Minbo, E-mail: minbolan@ecust.edu.cn [Shanghai Key Laboratory of Functional Materials Chemistry and Research Center of Analysis and Test, East China University of Science and Technology, Shanghai 200237 (China); State Key Laboratory of Bioreactor Engineering, East China University of Science and Technology, Shanghai 200237 (China)

    2016-02-15

    Highlights: • Antifouling PVP brushes were successfully grafted on PU films by SI-ATRP. • The effect of polymerization time on surface property and topography was studied. • Hydrophilicity and protein fouling resistance of PVP–PU films were greatly promoted. • Competitive adsorption of three proteins on PVP–PU films was evaluated. - Abstract: An anti-fouling surface of polyurethane (PU) film grafted with Poly(N-vinylpyrrolidone) (PVP) was prepared through surface-initiated atom transfer radical polymerization (SI-ATRP). And the polymerization time was investigated to obtain PU films with PVP brushes of different lengths. The surface properties and protein adsorption of modified PU films were evaluated. The results showed that the hydrophilicity of PU–PVP films were improved with the increase of polymerization time, which was not positive correlation with the surface roughness due to the brush structure. Additionally, the protein resistance performance was promoted when prolonging the polymerization time. The best antifouling PU–PVP (6.0 h) film reduced the adsoption level of bovine serum albumin (BSA), lysozyme (LYS), and brovin serum fibrinogen (BFG) by 93.4%, 68.3%, 85.6%, respectively, compared to the unmodified PU film. The competitive adsorption of three proteins indicated that LYS preferentially adsorbed on the modified PU film, while BFG had the lowest adsorption selectivity. And the amount of BFG on PU–PVP (6.0 h) film reduced greatly to 0.08 μg/cm{sup 2}, which was almost one-tenth of its adsorption from the single-protein system. Presented results suggested that both hydrophilicity and surface roughness might be the important factors in all cases of protein adsorption, and the competitive or selective adsorption might be related to the size of the proteins, especially on the non-charged films.

  17. Replacement of an oxo by an imido group in oxotransferase model compounds: influence on the oxygen atom transfer.

    Science.gov (United States)

    Mösch-Zanetti, Nadia C; Wurm, Dietmar; Volpe, Manuel; Lyashenko, Ganna; Harum, Bastian; Belaj, Ferdinand; Baumgartner, Judith

    2010-10-04

    Treatment of [MoO(N-t-Bu)Cl(2)(dme)] (dme = dimethoxyethane) with 2 equiv of the potassium salts of Schiff base ligands of the type KArNC(CH(3))CHC(CH(3))O afforded oxo imido molybdenum(VI) compounds [MoO(N-t-Bu)L(2)] {1, with Ar = phenyl (L(Ph)), 2 with Ar = 2-tolyl (L(MePh)), 3 with Ar = 2,6-dimethylphenyl (L(Me2Ph)) and 4 with Ar = 2,6-diisopropylphenyl (L(iPr2Ph))}. We have also prepared related bisimido complexes [Mo(N-t-Bu)(2)L(2) (5 with L = L(Ph), 6 with L = L(MePh), and 7 with L = L(Me2Ph)) by treatment of [Mo(N-t-Bu)(2)Cl(2)(dme)] with 2 equiv of the potassium salt of the respective ligand. 1, 3, 5, and 6 were characterized via single crystal X-ray diffraction. The oxo imido complexes exhibit oxygen atom transfer (OAT) reactivity toward trimethyl phosphine. Kinetic data were obtained for 1 and 3 by UV/vis spectroscopy revealing decreased OAT reactivity in comparison to related dioxo complexes with the same Schiff base ligands and decreased reactivity of 1 versus 3. Cyclic voltammetry was used to probe the electronic situation at the molybdenum center showing reversible reduction waves for 3 and [MoO(2)(L(Me2Ph))(2)] at comparable potentials while 1 exhibits a significant lower potential. Density functional theory (DFT) calculations showed a higher electron density on oxygen in the oxo imido complexes.

  18. Measurement of atomic electric fields and charge densities from average momentum transfers using scanning transmission electron microscopy.

    Science.gov (United States)

    Müller-Caspary, Knut; Krause, Florian F; Grieb, Tim; Löffler, Stefan; Schowalter, Marco; Béché, Armand; Galioit, Vincent; Marquardt, Dennis; Zweck, Josef; Schattschneider, Peter; Verbeeck, Johan; Rosenauer, Andreas

    2016-05-12

    This study sheds light on the prerequisites, possibilities, limitations and interpretation of high-resolution differential phase contrast (DPC) imaging in scanning transmission electron microscopy (STEM). We draw particular attention to the well-established DPC technique based on segmented annular detectors and its relation to recent developments based on pixelated detectors. These employ the expectation value of the momentum transfer as a reliable measure of the angular deflection of the STEM beam induced by an electric field in the specimen. The influence of scattering and propagation of electrons within the specimen is initially discussed separately and then treated in terms of a two-state channeling theory. A detailed simulation study of GaN is presented as a function of specimen thickness and bonding. It is found that bonding effects are rather detectable implicitly, e.g., by characteristics of the momentum flux in areas between the atoms than by directly mapping electric fields and charge densities. For strontium titanate, experimental charge densities are compared with simulations and discussed with respect to experimental artifacts such as scan noise. Finally, we consider practical issues such as figures of merit for spatial and momentum resolution, minimum electron dose, and the mapping of larger-scale, built-in electric fields by virtue of data averaged over a crystal unit cell. We find that the latter is possible for crystals with an inversion center. Concerning the optimal detector design, this study indicates that a sampling of 5mrad per pixel is sufficient in typical applications, corresponding to approximately 10×10 available pixels.

  19. Redox-inactive metal ions promoted the catalytic reactivity of non-heme manganese complexes towards oxygen atom transfer.

    Science.gov (United States)

    Choe, Cholho; Yang, Ling; Lv, Zhanao; Mo, Wanling; Chen, Zhuqi; Li, Guangxin; Yin, Guochuan

    2015-05-21

    Redox-inactive metal ions can modulate the reactivity of redox-active metal ions in a variety of biological and chemical oxidations. Many synthetic models have been developed to help address the elusive roles of these redox-inactive metal ions. Using a non-heme manganese(II) complex as the model, the influence of redox-inactive metal ions as a Lewis acid on its catalytic efficiency in oxygen atom transfer was investigated. In the absence of redox-inactive metal ions, the manganese(II) catalyst is very sluggish, for example, in cyclooctene epoxidation, providing only 9.9% conversion with 4.1% yield of epoxide. However, addition of 2 equiv. of Al(3+) to the manganese(II) catalyst sharply improves the epoxidation, providing up to 97.8% conversion with 91.4% yield of epoxide. EPR studies of the manganese(II) catalyst in the presence of an oxidant reveal a 16-line hyperfine structure centered at g = 2.0, clearly indicating the formation of a mixed valent di-μ-oxo-bridged diamond core, Mn(III)-(μ-O)2-Mn(IV). The presence of a Lewis acid like Al(3+) causes the dissociation of this diamond Mn(III)-(μ-O)2-Mn(IV) core to form monomeric manganese(iv) species which is responsible for improved epoxidation efficiency. This promotional effect has also been observed in other manganese complexes bearing various non-heme ligands. The findings presented here have provided a promising strategy to explore the catalytic reactivity of some di-μ-oxo-bridged complexes by adding non-redox metal ions to in situ dissociate those dimeric cores and may also provide clues to understand the mechanism of methane monooxygenase which has a similar diiron diamond core as the intermediate.

  20. Transferred multipolar atom model for 10β,17β-dihydroxy-17α-methylestr-4-en-3-one dihydrate obtained from the biotransformation of methyloestrenolone.

    Science.gov (United States)

    Faroque, Muhammad Umer; Yousuf, Sammer; Zafar, Salman; Choudhary, M Iqbal; Ahmed, Maqsood

    2016-05-01

    Biotransformation is the structural modification of compounds using enzymes as the catalysts and it plays a key role in the synthesis of pharmaceutically important compounds. 10β,17β-Dihydroxy-17α-methylestr-4-en-3-one dihydrate, C19H28O3·2H2O, was obtained from the fungal biotransformation of methyloestrenolone. The structure was refined using the classical independent atom model (IAM) and a transferred multipolar atom model using the ELMAM2 database. The results from the two refinements have been compared. The ELMAM2 refinement has been found to be superior in terms of the refinement statistics. It has been shown that certain electron-density-derived properties can be calculated on the basis of the transferred parameters for crystals which diffract to ordinary resolution.

  1. Predicting Radiative Heat Transfer in Oxy-Methane Flame Simulations: An Examination of Its Sensitivities to Chemistry and Radiative Property Models

    Directory of Open Access Journals (Sweden)

    Hassan Abdul-Sater

    2015-01-01

    Full Text Available Measurements from confined, laminar oxy-methane flames at different O2/CO2 dilution ratios in the oxidizer are first reported with measurements from methane-air flames included for comparison. Simulations of these flames employing appropriate chemistry and radiative property modeling options were performed to garner insights into the experimental trends and assess prediction sensitivities to the choice of modeling options. The chemistry was modeled employing a mixture-fraction based approach, Eddy dissipation concept (EDC, and refined global finite rate (FR models. Radiative properties were estimated employing four weighted-sum-of-gray-gases (WSGG models formulated from different spectroscopic/model databases. The mixture fraction and EDC models correctly predicted the trends in flame length and OH concentration variations, and the O2, CO2, and temperature measurements outside the flames. The refined FR chemistry model predictions of CO2 and O2 deviated from their measured values in the flame with 50% O2 in the oxidizer. Flame radiant power estimates varied by less than 10% between the mixture fraction and EDC models but more than 60% between the different WSGG models. The largest variations were attributed to the postcombustion gases in the temperature range 500 K–800 K in the upper sections of the furnace which also contributed significantly to the overall radiative transfer.

  2. ChemTrove: enabling a generic ELN to support chemistry through the use of transferable plug-ins and online data sources.

    Science.gov (United States)

    Day, Aileen E; Coles, Simon J; Bird, Colin L; Frey, Jeremy G; Whitby, Richard J; Tkachenko, Valery E; Williams, Antony J

    2015-03-23

    In designing an Electronic Lab Notebook (ELN), there is a balance to be struck between keeping it as general and multidisciplinary as possible for simplicity of use and maintenance and introducing more domain-specific functionality to increase its appeal to target research areas. Here, we describe the results of a collaboration between the Royal Society of Chemistry (RSC) and the University of Southampton, guided by the aims of the Dial-a-Molecule Grand Challenge, intended to achieve the best of both worlds and augment a discipline-agnostic ELN, LabTrove, with chemistry-specific functionality and using data provided by the ChemSpider platform. This has been done using plug-in technology to ensure maximum transferability with minimal effort of the chemistry functionality to other ELNs and equally other subject-specific functionality to LabTrove. The resulting product, ChemTrove, has undergone a usability trial by selected academics, and the resulting feedback will guide the future development of the underlying ELN technology.

  3. A cavity QED scheme for transferring of two-atom product state%传送两原子直积态的腔QED方案

    Institute of Scientific and Technical Information of China (English)

    吴韬; 何娟; 倪致祥; 叶柳

    2008-01-01

    本文提出一个基于原子和腔场共振相互作用传送未知原子直积态的腔QED方案,原子和腔场通过J-C哈密顿量发生共振相互作用.在这个方案里,我们只需要用两个原子接受被传送的原子态以及两个单模腔作为量子通道.该方案既不需要贝尔态测量,也不需要任何操作重构纠缠初态,并且传送成功的概率为100%.这个方案也可以推广到传送n个原子的直积态.%In this paper, we propose a simple scheme for transferring of a two-atom product state via cavity quantum electrodynamics. Our proposal is based on atom-cavity field resonant interaction, the atom interacts resonantly with the mode of the cavity according to the Jaynes-Cummings Hamiltonian. This proposal only requires two atoms for receiving the teleported state, and two cavities as the quantum channel. The scheme does not require performing any transformations to reconstruct the initial state and does not require Bell-state measurement. In addition, the transfer of the scheme has a successful probability of 100 percent in a simple manner. And the scheme can also be extended to transfer product state of n-atom.

  4. Mechanochemical Synthesis of Two Polymorphs of the Tetrathiafulvalene-Chloranil Charge Transfer Salt: An Experiment for Organic Chemistry

    Science.gov (United States)

    Wixtrom, Alex; Buhler, Jessica; Abdel-Fattah, Tarek

    2014-01-01

    Mechanochemical syntheses avoid or considerably reduce the use of reaction solvents, thus providing green chemistry synthetic alternatives that are both environmentally friendly and economically advantageous. The increased solid-state reactivity generated by mechanical energy imparted to the reactants by grinding or milling can offer alternative…

  5. Using Animations in Identifying General Chemistry Students' Misconceptions and Evaluating Their Knowledge Transfer Relating to Particle Position in Physical Changes

    Science.gov (United States)

    Smith, K. Christopher; Villarreal, Savannah

    2015-01-01

    This article reports on the types of views and misconceptions uncovered after assessing 155 freshman general chemistry students on the concept of particle position during the reversible physical change of melting, using the Melting Cycle Instrument, which illustrates particulate-level representations of a melting-freezing cycle. Animations…

  6. Transferability and reproducibility in electron-density studies--bond-topological and atomic properties of tripeptides of the type L-alanyl-X-L-alanine.

    Science.gov (United States)

    Grabowsky, Simon; Kalinowski, Roman; Weber, Manuela; Förster, Diana; Paulmann, Carsten; Luger, Peter

    2009-08-01

    In the last decade three different data bank approaches have been developed that are intended to make electron-density examinations of large biologically important molecules possible. They rely on Bader's concept of transferability of submolecular fragments with retention of their electronic properties. Therefore, elaborate studies on the quantification of transferability in experiment and theory are still very important. Tripeptides of the type L-alanyl-X-L-alanine (X being any of the 20 naturally encoded amino acids) serve as a model case between amino acids and proteins. The two experimental electron-density determinations (L-alanyl-L-histidinyl-L-alanine and L-alanyl-L-phenylalanyl-L-alanine, highly resolved synchrotron X-ray diffraction data sets) performed in this study and theoretical calculations on all 20 different L-alanyl-X-L-alanine molecules contribute to a better estimation of transferability in the peptide case. As a measure of reproducibility and transferability, standard deviations from averaging over bond-topological and atomic properties of atoms or bonds that are considered equal in their chemical environments were calculated. This way, transferability and reproducibility indices were introduced. It can be shown that experimental transferability indices generally slightly exceed experimental reproducibility indices and that these larger deviations can be attributed to chemical effects such as changes in the geometry (bond lengths and angles), the polarization pattern and the neighboring sphere due to crystal packing. These effects can partly be separated from each other and quantified with the help of gas-phase calculations at optimized and experimental geometries. Thus, the degree of transferability can be quantified in very narrow limits taking into account experimental errors and chemical effects.

  7. Importance of π-stacking interactions in the hydrogen atom transfer reactions from activated phenols to short-lived N-oxyl radicals.

    Science.gov (United States)

    Mazzonna, Marco; Bietti, Massimo; DiLabio, Gino A; Lanzalunga, Osvaldo; Salamone, Michela

    2014-06-06

    A kinetic study of the hydrogen atom transfer from activated phenols (2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols, 2,2,5,7,8-pentamethylchroman-6-ol, caffeic acid, and (+)-cathechin) to a series of N-oxyl radical (4-substituted phthalimide-N-oxyl radicals (4-X-PINO), 6-substituted benzotriazole-N-oxyl radicals (6-Y-BTNO), 3-quinazolin-4-one-N-oxyl radical (QONO), and 3-benzotriazin-4-one-N-oxyl radical (BONO)), was carried out by laser flash photolysis in CH3CN. A significant effect of the N-oxyl radical structure on the hydrogen transfer rate constants (kH) was observed with kH values that monotonically increase with increasing NO-H bond dissociation energy (BDENO-H) of the N-hydroxylamines. The analysis of the kinetic data coupled to the results of theoretical calculations indicates that these reactions proceed by a hydrogen atom transfer (HAT) mechanism where the N-oxyl radical and the phenolic aromatic rings adopt a π-stacked arrangement. Theoretical calculations also showed pronounced structural effects of the N-oxyl radicals on the charge transfer occurring in the π-stacked conformation. Comparison of the kH values measured in this study with those previously reported for hydrogen atom transfer to the cumylperoxyl radical indicates that 6-CH3-BTNO is the best N-oxyl radical to be used as a model for evaluating the radical scavenging ability of phenolic antioxidants.

  8. Atomic-Scale Design of Iron Fischer-Tropsch Catalysts; A Combined Computational Chemistry, Experimental, and Microkinetic Modeling Approach

    Energy Technology Data Exchange (ETDEWEB)

    Manos Mavrikakis; James Dumesic; Rahul Nabar; Calvin Bartholonew; Hu Zou; Uchenna Paul

    2008-09-29

    measurements. The results provide a platform for further development of microkinetic models of FTS on Fe and a basis for more precise modeling of FTS activity of Fe catalysts. Calculations using periodic, self-consistent Density Functional Theory (DFT) methods were performed on various realistic models of industrial, Fe-based FTS catalysts. Close-packed, most stable Fe(110) facet was analyzed and subsequently carbide formation was found to be facile leading to the choice of the FeC(110) model representing a Fe facet with a sub-surface C atom. The Pt adatom (Fe{sup Pt}(110)) was found to be the most stable model for our studies into Pt promotion and finally the role of steps was elucidated by recourse to the defected Fe(211) facet. Binding Energies(BEs), preferred adsorption sites and geometries for all FTS relevant stable species and intermediates were evaluated on each model catalyst facet. A mechanistic model (comprising of 32 elementary steps involving 19 species) was constructed and each elementary step therein was fully characterized with respect to its thermochemistry and kinetics. Kinetic calculations involved evaluation of the Minimum Energy Pathways (MEPs) and activation energies (barriers) for each step. Vibrational frequencies were evaluated for the preferred adsorption configuration of each species with the aim of evaluating entropy-changes, pre exponential factors and serving as a useful connection with experimental surface science techniques. Comparative analysis among these four facets revealed important trends in their relative behavior and roles in FTS catalysis. Overall the First Principles Calculations afforded us a new insight into FTS catalysis on Fe and modified-Fe catalysts.

  9. Chemistry of americium

    Energy Technology Data Exchange (ETDEWEB)

    Schulz, W.W.

    1976-01-01

    Essential features of the descriptive chemistry of americium are reviewed. Chapter titles are: discovery, atomic and nuclear properties, collateral reading, production and uses, chemistry in aqueous solution, metal, alloys, and compounds, and, recovery, separation, purification. Author and subject indexes are included. (JCB)

  10. Steric Effect for Proton, Hydrogen-Atom, andHydride Transfer Reactions with Geometric Isomers of NADH-Model Ruthenium Complexes

    Energy Technology Data Exchange (ETDEWEB)

    Fujita E.; Cohen, B.W.; Polyansky, D.E.; Achord, P.; Cabelli, D.; Muckerman, J.T.; Tanaka, K.; Thummel, R.P.; Zong, R.

    2012-01-01

    Two isomers, [Ru(1)]{sup 2+} (Ru = Ru(bpy){sub 2}, bpy = 2,2{prime}-bipyridine, 1 = 2-(pyrid-2{prime}-yl)-1-azaacridine) and [Ru(2)]{sup 2+} (2 = 3-(pyrid-2{prime}-yl)-4-azaacridine), are bio-inspired model compounds containing the nicotinamide functionality and can serve as precursors for the photogeneration of C-H hydrides for studying reactions pertinent to the photochemical reduction of metal-C{sub 1} complexes and/or carbon dioxide. While it has been shown that the structural differences between the azaacridine ligands of [Ru(1)]{sup 2+} and [Ru(2)]{sup 2+} have a significant effect on the mechanism of formation of the hydride donors, [Ru(1HH)]{sup 2+} and [Ru(2HH)]{sup 2+}, in aqueous solution, we describe the steric implications for proton, net-hydrogen-atom and net-hydride transfer reactions in this work. Protonation of [Ru(2{sup {sm_bullet}-})]{sup +} in aprotic and even protic media is slow compared to that of [Ru(1{sup {sm_bullet}-})]{sup +}. The net hydrogen-atom transfer between *[Ru(1)]{sup 2+} and hydroquinone (H{sub 2}Q) proceeds by one-step EPT, rather than stepwise electron-proton transfer. Such a reaction was not observed for *[Ru(2)]{sup 2+} because the non-coordinated N atom is not easily available for an interaction with H{sub 2}Q. Finally, the rate of the net hydride ion transfer from [Ru(1HH)]{sup 2+} to [Ph{sub 3}C]{sup +} is significantly slower than that of [Ru(2HH)]{sup 2+} owing to steric congestion at the donor site.

  11. Oxygen-Induced Restructuring of Rutile TiO(2)(110): Formation Mechanism, Atomic Models, and Influence on Surface Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Li, Min; Hebenstreit, Wilhelm; Diebold, Ulrike; Henderson, Michael A.; Jennison, Dwight R.

    1999-07-07

    The rutile TiO{sub 2} (110) (1x1) surface is considered the prototypical ''well-defined'' system in the surface science of metal oxides. Its popularity results partly from two experimental advantages: bulk-reduced single crystals do not exhibit charging, and stoichiometric surfaces--as judged by electron spectroscopes--can be prepared reproducibly by sputtering and annealing in oxygen. We present results that show that this commonly-applied preparation procedure may result in a surface structure that is by far more complex than generally anticipated. Flat, (1x1) terminated surfaces are obtained by sputtering and annealing in ultrahigh vacuum. When re-annealed in oxygen at moderate temperatures (470 K to 660 K), irregular networks of partially-connected, pseudohexagonal rosettes (6.5 x 6 {angstrom} wide), one-unit cell wide strands, and small ({approximately} tens of {angstrom}) (1x1) islands appear. This new surface phase is formed through reaction of oxygen gas with interstitial Ti from the reduced bulk. Because it consists of an incomplete, kinetically-limited (1x1) layer, this phenomenon has been termed restructuring. We report a combined experimental and theoretical study that systematically explores this restructuring process. The influence of several parameters (annealing time, temperature, pressure, sample history, gas) on the surface morphology is investigated using STM. The surface coverage of the added phase as well as the kinetics of the restructuring process are quantified by LEIS and SSIMS measurements in combination with annealing in {sup 18}O-enriched gas. Atomic models of the essential structural elements are presented and are shown to be stable with first-principles density functional calculations. The effect of oxygen-induced restructuring on surface chemistry and its importance for TiO{sub 2} and other bulk-reduced oxide materials is briefly discussed.

  12. Electronic Origins of the Variable Efficiency of Room-Temperature Methane Activation by Homo- and Heteronuclear Cluster Oxide Cations [XYO2](+) (X, Y = Al, Si, Mg): Competition between Proton-Coupled Electron Transfer and Hydrogen-Atom Transfer.

    Science.gov (United States)

    Li, Jilai; Zhou, Shaodong; Zhang, Jun; Schlangen, Maria; Weiske, Thomas; Usharani, Dandamudi; Shaik, Sason; Schwarz, Helmut

    2016-06-29

    The reactivity of the homo- and heteronuclear oxide clusters [XYO2](+) (X, Y = Al, Si, Mg) toward methane was studied using Fourier transform ion cyclotron resonance mass spectrometry, in conjunction with high-level quantum mechanical calculations. The most reactive cluster by both experiment and theory is [Al2O2](•+). In its favorable pathway, this cluster abstracts a hydrogen atom by means of proton-coupled electron transfer (PCET) instead of following the conventional hydrogen-atom transfer (HAT) route. This mechanistic choice originates in the strong Lewis acidity of the aluminum site of [Al2O2](•+), which cleaves the C-H bond heterolytically to form an Al-CH3 entity, while the proton is transferred to the bridging oxygen atom of the cluster ion. In addition, a comparison of the reactivity of heteronuclear and homonuclear oxide clusters [XYO2](+) (X, Y = Al, Si, Mg) reveals a striking doping effect by aluminum. Thus, the vacant s-p hybrid orbital on Al acts as an acceptor of the electron pair from methyl anion (CH3(-)) and is therefore eminently important for bringing about thermal methane activation by PCET. For the Al-doped cluster ions, the spin density at an oxygen atom, which is crucial for the HAT mechanism, acts here as a spectator during the course of the PCET mediated C-H bond cleavage. A diagnostic plot of the deformation energy vis-à-vis the barrier shows the different HAT/PCET reactivity map for the entire series. This is a strong connection to the recently discussed mechanism of oxidative coupling of methane on magnesium oxide surfaces proceeding through Grignard-type intermediates.

  13. Investigation of the Mechanism of Electron Capture and Electron Transfer Dissociation of Peptides with a Covalently Attached Free Radical Hydrogen Atom Scavenger.

    Science.gov (United States)

    Sohn, Chang Ho; Yin, Sheng; Peng, Ivory; Loo, Joseph A; Beauchamp, J L

    2015-11-15

    The mechanisms of electron capture and electron transfer dissociation (ECD and ETD) are investigated by covalently attaching a free-radical hydrogen atom scavenger to a peptide. The 2,2,6,6-tetramethylpiperidin-l-oxyl (TEMPO) radical was chosen as the scavenger due to its high hydrogen atom affinity (ca. 280 kJ/mol) and low electron affinity (ca. 0.45 ev), and was derivatized to the model peptide, FQX(TEMPO)EEQQQTEDELQDK. The X(TEMPO) residue represents a cysteinyl residue derivatized with an acetamido-TEMPO group. The acetamide group without TEMPO was also examined as a control. The gas phase proton affinity (882 kJ/mol) of TEMPO is similar to backbone amide carbonyls (889 kJ/mol), minimizing perturbation to internal solvation and sites of protonation of the derivatized peptides. Collision induced dissociation (CID) of the TEMPO tagged peptide dication generated stable odd-electron b and y type ions without indication of any TEMPO radical induced fragmentation initiated by hydrogen abstraction. The type and abundance of fragment ions observed in the CID spectra of the TEMPO and acetamide tagged peptides are very similar. However, ECD of the TEMPO labeled peptide dication yielded no backbone cleavage. We propose that a labile hydrogen atom in the charge reduced radical ions is scavenged by the TEMPO radical moiety, resulting in inhibition of N-Cα backbone cleavage processes. Supplemental activation after electron attachment (ETcaD) and CID of the charge-reduced precursor ion generated by electron transfer of the TEMPO tagged peptide dication produced a series of b + H (b(H)) and y + H (y(H)) ions along with some c ions having suppressed intensities, consistent with stable O-H bond formation at the TEMPO group. In summary, the results indicate that ECD and ETD backbone cleavage processes are inhibited by scavenging of a labile hydrogen atom by the localized TEMPO radical moiety. This observation supports the conjecture that ECD and ETD processes involve long

  14. Computationally Efficient Assessments of the Effects of Radiative Transfer, Turbulence Radiation Interactions, and Finite Rate Chemistry in the Mach 20 Reentry F Flight Vehicle

    Directory of Open Access Journals (Sweden)

    Gautham Krishnamoorthy

    2016-01-01

    Full Text Available Effects of finite rate chemistry, radiative heat transfer, and turbulence radiation interactions (TRI are assessed in a fully coupled manner in simulations of the Mach 20 Reentry F flight vehicle. Add-on functions were employed to compute a Planck mean absorption coefficient and the temperature self-correlation term (for TRI effects in the optically thin shock layer. Transition onset was induced by specifying a wall roughness height at the experimentally observed transition location. The chemistry was modeled employing eight elementary reactions and an equilibrium approach allowing species to relax towards their chemical equilibrium values over the process characteristic time scale. The wall heat fluxes in the turbulent region, density, and velocity profiles compared reasonably well against measurements as well as similar calculations reported previously. The density predictions were more sensitive to the choice of modeling options than the velocities. The radiative source term magnitude agreed closely with its measurements deduced from shock tube experiments. The TRI model predicted a 60% enhancement in emission due to temperature fluctuations in the turbulent boundary layer. While the variations in density and velocity predictions among the models diminished along the length of the body, the O and NO prediction variations extended well into the turbulent boundary layer.

  15. Interfacial chemistry and the design of solid-phase nucleic acid hybridization assays using immobilized quantum dots as donors in fluorescence resonance energy transfer.

    Science.gov (United States)

    Algar, W Russ; Krull, Ulrich J

    2011-01-01

    The use of quantum dots (QDs) as donors in fluorescence resonance energy transfer (FRET) offer several advantages for the development of multiplexed solid-phase QD-FRET nucleic acid hybridization assays. Designs for multiplexing have been demonstrated, but important challenges remain in the optimization of these systems. In this work, we identify several strategies based on the design of interfacial chemistry for improving sensitivity, obtaining lower limits of detection (LOD) and enabling the regeneration and reuse of solid-phase QD-FRET hybridization assays. FRET-sensitized emission from acceptor dyes associated with hybridization events at immobilized QD donors provides the analytical signal in these assays. The minimization of active sensing area reduces background from QD donor PL and allows the resolution of smaller amounts of acceptor emission, thus lowering the LOD. The association of multiple acceptor dyes with each hybridization event can enhance FRET efficiency, thereby improving sensitivity. Many previous studies have used interfacial protein layers to generate selectivity; however, transient destabilization of these layers is shown to prevent efficient regeneration. To this end, we report a protein-free interfacial chemistry and demonstrate the specific detection of as little as 2 pmol of target, as well as an improved capacity for regeneration.

  16. Low-Scaling Quantum Chemistry Approach to Excited-State Properties via an ab Initio Exciton Model: Application to Excitation Energy Transfer in a Self-Assembled Nanotube.

    Science.gov (United States)

    Morrison, Adrian F; Herbert, John M

    2015-11-05

    We introduce a charge-embedding scheme for an excited-state quantum chemistry method aimed at weakly interacting molecular aggregates. The Hamiltonian matrix for the aggregate is constructed in a basis of direct products of configuration-state functions for the monomers, and diagonalization of this matrix affords excitation energies within ∼0.2 eV of the corresponding supersystem calculation. Both the basis states and the coupling matrix elements can be computed in a distributed way, resulting in an algorithm whose time-to-solution is independent of the number of chromophores, and we report calculations on systems with almost 55 000 basis functions using fewer than 450 processors. In a semiconducting organic nanotube, we find evidence of ultrafast, coherent dynamics followed by energy localization driven by static disorder. Truncation of the model system has a qualitative effect on the energy-transfer dynamics, demonstrating the importance of simulating an extended portion of the nanotube, which is not feasible using traditional quantum chemistry.

  17. Electron density characteristics and charge transfer effect of hydrogen bond O-H···Pt(II): atoms in molecules study and natural bond orbital analysis

    Science.gov (United States)

    Zhang, Guiqiu; Li, Xiwen; Li, Yan; Chen, Dezhan

    2013-11-01

    In this report, we extended the works of Rizzato et al. [Angew. Chem. Int. Ed. 49, 7440 (2010)] on the nature of O-H...Pt hydrogen bond in trans-[PtCl2(NH3)(N-glycine)].H2O(1.H2O) complex, by computational study of O-H...Pt interaction in [NBu4][Pt(C6F5)3(8-hydroxyquinaldine)], with emphasis on charge transfer effect in this interaction of platinum(II) and hydrogen atom. According to the crystallographic geometry reported by José María Casas et al., [NBu4][Pt(C6F5)3(8-hydroxyquinaldine)] possesses one O-H...Pt hydrogen bridging interaction, similar to the case in trans-[PtCl2(NH3)(N-glycine)].H2O(1.H2O) complex. On the basis of topological criteria of electron density, we characterised this O-H...Pt interaction. Charge transferred between platinum(II) and σ*O-H orbital in this complex was calculated by using NBO method. The stabilised energy associated to charge transfer was estimated using a direct proportionality, that is 2-3 eV per electron transferred. Charge transfer effects in O-H...Pt hydrogen bonds were studied for these two complexes. Our results indicate that the interaction of O-H...Pt is closed-shell in nature with significant charge transfer, and that charge transfer effect is not negligible in the interaction of O-H...Pt. The second conclusion is different from the result of Rizzato et al.

  18. NUCLEAR CHEMISTRY ANNUAL REPORT 1970

    Energy Technology Data Exchange (ETDEWEB)

    Authors, Various

    1971-05-01

    Papers are presented for the following topics: (1) Nuclear Structure and Nuclear Properties - (a) Nuclear Spectroscopy and Radioactivity; (b) Nuclear Reactions and Scattering; (c) Nuclear Theory; and (d) Fission. (2) Chemical and Atomic Physics - (a) Atomic and Molecular Spectroscopy; and (b) Hyperfine Interactions. (3) Physical, Inorganic, and Analytical Chemistry - (a) X-Ray Crystallography; (b) Physical and Inorganic Chemistry; (c) Radiation Chemistry; and (d) Chemical Engineering. (4) Instrumentation and Systems Development.

  19. Mechanistic aspects of gas-phase hydrogen-atom transfer from methane to [CO](·+) and [SiO](·+) : why do they differ?

    Science.gov (United States)

    Dietl, Nicolas; Troiani, Anna; Schlangen, Maria; Ursini, Ornella; Angelini, Giancarlo; Apeloig, Yitzhak; de Petris, Giulia; Schwarz, Helmut

    2013-05-17

    The reactivity of the two diatomic congeneric systems [CO](·+) and [SiO](·+) towards methane has been investigated by means of mass spectrometry and quantum-chemical calculations. While [CO](·+) gives rise to three different reaction channels, [SiO](·+) reacts only by hydrogen-atom transfer (HAT) from methane under thermal conditions. A theoretical analysis of the respective HAT processes reveals two distinctly different mechanistic pathways for [CO](·+) and [SiO](·+), and a comparison to the higher metal oxides of Group 14 emphasizes the particular role of carbon as a second-row p element.

  20. Evidence for a Precursor Complex in C-H Hydrogen Atom Transfer Reactions Mediated by a Manganese(IV) Oxo Complex

    OpenAIRE

    Garcia Bosch, Isaac; Company Casadevall, Anna; Cady, Clyde W.; Styring, Stenbjörn; Browne, Wesley R; Ribas Salamaña, Xavi; Costas Salgueiro, Miquel

    2011-01-01

    HAT trick: [MnIV(OH)2(H,MePytacn)]2+ (A) and [MnIV(O)(OH)(H,MePytacn)]+ (B) differ in their reactions with CH bonds: compound A engages in typical single-step hydrogen atom transfer (HAT) reactions, whereas B first forms a substrate–B encounter complex (C; see scheme). This equilibrium alters the relative CH reactivity from that expected from CH bond dissociation energies Aquest mateix article està publicat a l'edició alemanya d''Angewandte Chemie' (ISSN 0044-8249, EISSN 1521-3757), 2011, ...

  1. A DFT Study of R-X Bond Dissociation Enthalpies of Relevance to the Initiation Process of Atom Transfer Radical Polymerization

    DEFF Research Database (Denmark)

    Gillies, Malcolm Bjørn; Matyjaszewski, Krzysztof; Norrby, Per-Ola

    2003-01-01

    DFT calculations at the B3P86/6-31G** level have been carried out to derive the bond dissociation energies (BDE) and free energies for a number of R-X systems (X ) Cl, Br, I, N3, and S2-CNMe2) that have been or can potentially be used as initiators for atom transfer radical polymerization (ATRP......). For selected systems, a conformational search was carried out for R-X and R by using semiempirical (PM3) and molecular mechanics (MM+ augmented with appropriately optimized parameters for the radical systems) methods. The MM+ technique is more suited to search for the most stable conformations. The computed...

  2. Facile Preparation of Crosslinked Polymeric Nanocapsules via Combination of Surface-Initiated Atom Transfer Radical Polymerization and Ultraviolet Irradiated Crosslinking Techniques

    Directory of Open Access Journals (Sweden)

    Mu Bin

    2009-01-01

    Full Text Available Abstract A facile approach for the preparation of crosslinked polymeric nanocapsules was developed by the combination of the surface-initiated atom transfer radical polymerization and ultraviolet irradiation crosslinking techniques. The well-defined polystyrene grafted silica nanoparticles were prepared via the SI-ATRP of styrene from functionalized silica nanoparticles. Then the grafted polystyrene chains were crosslinked with ultraviolet irradiation. The cross-linked polystyrene nanocapsules with diameter of 20–50 nm were achieved after the etching of the silica nanoparticle templates with hydrofluoric acid. The strategy developed was confirmed with Fourier transform infrared, thermogravimetric analysis, and transmission electron microscopy.

  3. The Transfer of Atoms, Ions and Molecular Groups in Solution. Part 3. Monte Carlo Methods for the Evaluation of Rate Constants.

    Science.gov (United States)

    1983-10-31

    tranal. Sykes and Bell) pp. 342-51 12. J. M. McKinley and P. P. Schmidt, Che. Phys. Letters, submitted. and ref. (4) 13. G. Arfken . Mathematical Methods ...Transfer of Atoms, Ions and Molecular Groups Nf in Solution.III. Monte Carlo methods for the evaluation of rate constants I by P. P. Schmidt Prepared...technical Groups in Solution.poilI. Monte Carlo methods for the evaluation of rate a. PERFORMING ORG. REPORT NUMBER congtant 7, AUTHOR(e) B. CONTRACT Oft

  4. Efficient Cu-catalyzed atom transfer radical addition reactions of fluoroalkylsulfonyl chlorides with electron-deficient alkenes induced by visible light.

    Science.gov (United States)

    Tang, Xiao-Jun; Dolbier, William R

    2015-03-27

    Fluoroalkylsulfonyl chlorides, R(f)SO2Cl, in which R(f)=CF3, C4F9, CF2H, CH2F, and CH2CF3, are used as a source of fluorinated radicals to add fluoroalkyl groups to electron-deficient, unsaturated carbonyl compounds. Photochemical conditions, using Cu mediation, are used to produce the respective α-chloro-β-fluoroalkylcarbonyl products in excellent yields through an atom transfer radical addition (ATRA) process. Facile nucleophilic replacement of the α-chloro substituent is shown to lead to further diverse functionalization of the products. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Reactions of the cumyloxyl radical with secondary amides. The influence of steric and stereoelectronic effects on the hydrogen atom transfer reactivity and selectivity.

    Science.gov (United States)

    Salamone, Michela; Basili, Federica; Mele, Riccardo; Cianfanelli, Marco; Bietti, Massimo

    2014-12-19

    A time-resolved kinetic study of the hydrogen atom transfer (HAT) reactions from secondary alkanamides to the cumyloxyl radical was carried out in acetonitrile. HAT predominantly occurs from the N-alkyl α-C-H bonds, and a >60-fold decrease in kH was observed by increasing the steric hindrance of the acyl and N-alkyl groups. The role of steric and stereoelectronic effects on the reactivity and selectivity is discussed in the framework of HAT reactions from peptides.

  6. Kinetic Study of the Reaction of the Phthalimide-N-oxyl Radical with Amides: Structural and Medium Effects on the Hydrogen Atom Transfer Reactivity and Selectivity.

    Science.gov (United States)

    Bietti, Massimo; Forcina, Veronica; Lanzalunga, Osvaldo; Lapi, Andrea; Martin, Teo; Mazzonna, Marco; Salamone, Michela

    2016-12-02

    A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of secondary N-(4-X-benzyl)acetamides and tertiary amides to the phthalimide-N-oxyl radical (PINO) has been carried out. The results indicate that HAT is strongly influenced by structural and medium effects; in particular, the addition of Brønsted and Lewis acids determines a significant deactivation of C-H bonds α to the amide nitrogen of these substrates. Thus, by changing the reaction medium, it is possible to carefully control the regioselectivity of the aerobic oxidation of amides catalyzed by N-hydroxyphthalimide, widening the synthetic versatility of this process.

  7. Partial Characterization of a Novel Amphibian Hemoglobin as a Model for Graduate Student Investigation on Peptide Chemistry, Mass Spectrometry, and Atomic Force Microscopy

    Science.gov (United States)

    Bemquerer, Marcelo P.; Macedo, Jessica K. A.; Ribeiro, Ana Carolina J.; Carvalho, Andrea C.; Silva, Debora O. C.; Braz, Juliana M.; Medeiros, Kelliane A.; Sallet, Lunalva A. P.; Campos, Pollyanna F.; Prates, Maura V.; Silva, Luciano P.

    2012-01-01

    Graduate students in chemistry, and in biological and biomedical fields must learn the fundamentals and practices of peptide and protein chemistry as early as possible. A project-oriented approach was conducted by first-year M.Sc and Ph.D students in biological sciences. A blind glass slide containing a cellular smear and an aqueous cellular…

  8. Partial Characterization of a Novel Amphibian Hemoglobin as a Model for Graduate Student Investigation on Peptide Chemistry, Mass Spectrometry, and Atomic Force Microscopy

    Science.gov (United States)

    Bemquerer, Marcelo P.; Macedo, Jessica K. A.; Ribeiro, Ana Carolina J.; Carvalho, Andrea C.; Silva, Debora O. C.; Braz, Juliana M.; Medeiros, Kelliane A.; Sallet, Lunalva A. P.; Campos, Pollyanna F.; Prates, Maura V.; Silva, Luciano P.

    2012-01-01

    Graduate students in chemistry, and in biological and biomedical fields must learn the fundamentals and practices of peptide and protein chemistry as early as possible. A project-oriented approach was conducted by first-year M.Sc and Ph.D students in biological sciences. A blind glass slide containing a cellular smear and an aqueous cellular…

  9. Antioxidant activities of [60]fullerene derivatives from chalcone, flavone and flavanone: A ONIOM approach via H-atom and electron transfer mechanism

    Science.gov (United States)

    Thong, Nguyen Minh; Dao, Duy Quang; Ngo, Thi Chinh; Huyen, Trinh Le; Nam, Pham Cam

    2016-05-01

    Antioxidant properties of C60 flavonoid conjugates were computationally examined via their O-H bond dissociation enthalpies (BDEs) and ionization energies (IEs) using two-layer ONIOM and PM6 methods, respectively. Eight ONIOM((RO)B3LYP/6-311++G(2df,2p):PM6) models were evaluated by computing BDE(O-H)s of a series of polyphenol. Synthetic mechanism of C60 flavonoid conjugates was also explored via the potential energy surfaces of reaction between C60 and malonate flavonoid derivatives (chalcone, flavone and flavanone) at the B3LYP/6-31G(d)//PM6. Antioxidant activities of C60 flavonoid conjugates were discussed via hydrogen atom transfer, single electron transfer mechanisms and the effect of C60 on the BDE(O-H)s and IEs of these compounds.

  10. Scheme to transfer an atomic entangled state in cavity QED%一个传送原子纠缠态的新方案

    Institute of Scientific and Technical Information of China (English)

    吴韬; 叶柳; 倪致祥

    2007-01-01

    We present a scheme for transferring an unknown atomic entangled state via atom-cavity field interaction. This proposal , which has success probability of unit , is mainly employing two atoms for receiving the teleported state, and a two- mode cavity as the quantum channel. The two modes of the cavity have different frequencies and polarizations. So the two modes are distinguished by their frequencies and their orthogonal polarizations, hence they occupy distinct regions in the cavity. The atom interacts resonantly with the mode of the cavity according to the Jaynes-Cummings Hamiltonian, and when interaction between the atom and one of-the two modes takes place, the other mode remains unaffected. This scheme does not require Bell-state measurement and any operations to reconstruct the initial state. This scheme can also be extended to transfer entangled state of N-atom.%本文提出一个通过原子和腔场相互作用传送未知原子纠缠态的新方案,并且成功概率为100%.在这个方案里,我们主要利用两个原子用来接受被传送的原子纠缠态以及一个双模腔作为量子通道.由于腔场的两个模具有不同的频率和正交极化,因此这两个模能够被区分,并且处于腔场的不同区域.原子和腔场通过J-C哈密顿量发生共振相互作用,当原子和其中一个模相互作用时,另外一个模不受影响.该方案既不需要贝尔态测量,也不需要任何操作重构纠缠初态.这个方案也可以推广到传送N个原子的纠缠态.

  11. Metal-Free Hydrogen Atom Transfer from Water: Expeditious Hydrogenation of N-Heterocycles Mediated by Diboronic Acid.

    Science.gov (United States)

    Xia, Yun-Tao; Sun, Xiao-Tao; Zhang, Ling; Luo, Kai; Wu, Lei

    2016-11-21

    A hydrogenation of N-heterocycles mediated by diboronic acid with water as the hydrogen atom source is reported. A variety of N-heterocycles can be hydrogenated with medium to excellent yields within 10 min. Complete deuterium incorporation from stoichiometric D2 O onto substrates further exemplifies the H/D atom sources. Mechanism studies reveal that the reduction proceeds with initial 1,2-addition, in which diboronic acid synergistically activates substrates and water via a six-membered ring transition state.

  12. 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.

  13. Fluorescence resonance energy transfer (FRET) in chemistry and biology: Non-Förster distance dependence of the FRET rate

    Indian Academy of Sciences (India)

    Sangeeta Saini; Harjinder Singh; Biman Bagchi

    2006-01-01

    Fluorescence resonance energy transfer (FRET) is a popular tool to study equilibrium and dynamical properties of polymers and biopolymers in condensed phases and is now widely used in conjunction with single molecule spectroscopy. In the data analysis, one usually employs the Förster expression which predicts (1/6) distance dependence of the energy transfer rate. However, critical analysis shows that this expression can be of rather limited validity in many cases. We demonstrate this by explicitly considering a donor-acceptor system, polyfluorene (PF6)-tetraphenylporphyrin (TPP), where the size of both donor and acceptor is comparable to the distance separating them. In such cases, one may expect much weaker distance (as 1/2 or even weaker) dependence. We have also considered the case of energy transfer from a dye to a nanoparticle. Here we find 1/4 distance dependence at large separations, completely different from Förster. We also discuss recent application of FRET to study polymer conformational dynamics.

  14. Shape-selective catalysts for Fischer-Tropsch chemistry : atomic layer deposition of active catalytic metals. Activity report : January 1, 2005 - September 30, 2005.

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-04-15

    Argonne National Laboratory is carrying 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 is desirable that the catalysts have high selectivity and stability with respect to both mechanical strength and aging properties. The broad goal is to produce diesel fraction components and avoiding excess yields of both light hydrocarbons and heavy waxes. Originally the goal was to prepare shape-selective catalysts that would limit the formation of long-chain products and yet retain the active metal sites in a protected 'cage.' Such catalysts were prepared with silica-containing fractal cages. The activity was essentially the same as that of catalysts without the cages. We are currently awaiting follow-up experiments to determine the attrition strength of these catalysts. 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 complete monolayer coverage. In addition, there was likely to be significant variation in the Fe and Ru loading among the membranes due to difficulties in nucleating these materials on the aluminum oxide

  15. Presidential Green Chemistry Challenge: 1998 Academic Award (Trost)

    Science.gov (United States)

    Presidential Green Chemistry Challenge 1998 award winner Professor Barry M. Trost, developed the concept of atom economy: chemical reactions that do not waste atoms. This is a fundamental cornerstone of green chemistry.

  16. Electron transfer and atom exchange between aqueous Fe(II) and structural Fe(III) in clays. Role in U and Hg(II) transformations

    Energy Technology Data Exchange (ETDEWEB)

    Scherer, Michelle [Univ. of Iowa, Iowa City, IA (United States)

    2016-08-31

    During this project, we investigated Fe electron transfer and atom exchange between aqueous Fe(II) and structural Fe(III) in clay minerals. We used selective chemical extractions, enriched Fe isotope tracer experiments, computational molecular modeling, and Mössbauer spectroscopy. Our findings indicate that structural Fe(III) in clay minerals is reduced by aqueous Fe(II) and that electron transfer occurs when Fe(II) is sorbed to either basal planes and edge OH-groups of clay mineral. Findings from highly enriched isotope experiments suggest that up to 30 % of the Fe atoms in the structure of some clay minerals exhanges with aqueous Fe(II). First principles calculations using a small polaron hopping approach suggest surprisingly fast electron mobility at room temperature in a nontronite clay mineral and are consistent with temperature dependent Mössbauer data Fast electron mobility suggests that electrons may be able to conduct through the mineral fast enough to enable exchange of Fe between the aqueous phase and clay mineral structure. over the time periods we observed. Our findings suggest that Fe in clay minerals is not as stable as previously thought.

  17. The Place of Macromolecules in Freshman Chemistry

    Science.gov (United States)

    Wunderlich, Bernhard

    1973-01-01

    Discusses the inclusion of knowledge on macromolecules into a freshman chemistry course which emphasizes topics in organic chemistry, polymer science and biochemistry, atoms, chemical thermodynamics, and inorganic chemistry. Indicates that the program is the only way to keep chemistry education up to date. (CC)

  18. Photoresponsive Azopolyester–PMMA Block Copolymers Obtained by Combination of ATRP, Polycondensation, and “Click” Chemistry

    DEFF Research Database (Denmark)

    Berges, Cristina; Javakhishvili, Irakli; Hvilsted, Søren

    2012-01-01

    Novel azobenzene‐containing block copolymers (BCs) with a polyester block bearing azobenzene moieties in the side chain and a poly (methyl methacrylate) (PMMA) block have been synthesized by the combination of atom transfer radical polymerization (ATRP), polycondensation, and “click” chemistry. T...

  19. A new type of excited-state intramolecular proton transfer: proton transfer from phenol OH to a carbon atom of an aromatic ring observed for 2-phenylphenol.

    Science.gov (United States)

    Lukeman, Matthew; Wan, Peter

    2002-08-14

    The photochemical deuterium incorporation at the 2'- and 4'-positions of 2-phenylphenol (4) and equivalent positions of related compounds has been studied in D(2)O (CH(3)OD)-CH(3)CN solutions with varying D(2)O (CH(3)OD) content. Predominant exchange was observed at the 2'-position with an efficiency that is independent of D(2)O (MeOD) content. Exchange at the 2'-position (but not at the 4'-position) was also observed when crystalline samples of 4-OD were irradiated. Data are presented consistent with a mechanism of exchange that involves excited-state intramolecular proton transfer (ESIPT) from the phenol to the 2'-carbon position of the benzene ring not containing the phenol, to generate the corresponding keto tautomer (an o-quinone methide). This is the first explicit example of a new class of ESIPT in which an acidic phenolic proton is transferred to an sp(2)-hybridized carbon of an aromatic ring. The complete lack of exchange observed for related substrates 6-9 and for planar 4-hydroxyfluorene (10) is consistent with a mechanism of ESIPT that requires an initial hydrogen bonding interaction between the phenol proton and the benzene pi-system. Similar exchange was observed for 2,2'-biphenol (5), suggesting that this new type of ESIPT is a general reaction for unconstrained 2'-aryl-substituted phenols and other related hydroxyarenes.

  20. Atomic scattering in the diffraction limit: electron transfer in keV Li+-Na(3s, 3p) collisions

    DEFF Research Database (Denmark)

    Poel, Mike van der; Nielsen, C.V.; Rybaltover, M.

    2002-01-01

    We measure angle differential cross sections (DCS) in Li+ + Na --> Li + Na+ electron transfer collisions in the 2.7-24 keV energy range. We do this with a newly constructed apparatus which combines the experimental technique of cold target recoil ion momentum spectroscopy with a laser-cooled target...

  1. When Atoms Want

    Science.gov (United States)

    Talanquer, Vicente

    2013-01-01

    Chemistry students and teachers often explain the chemical reactivity of atoms, molecules, and chemical substances in terms of purposes or needs (e.g., atoms want or need to gain, lose, or share electrons in order to become more stable). These teleological explanations seem to have pedagogical value as they help students understand and use…

  2. When Atoms Want

    Science.gov (United States)

    Talanquer, Vicente

    2013-01-01

    Chemistry students and teachers often explain the chemical reactivity of atoms, molecules, and chemical substances in terms of purposes or needs (e.g., atoms want or need to gain, lose, or share electrons in order to become more stable). These teleological explanations seem to have pedagogical value as they help students understand and use…

  3. Unusually Slow Electron Cooling to Charge-Transfer State in Gradient CdTeSe Alloy Nanocrystals Mediated through Mn Atom.

    Science.gov (United States)

    Debnath, Tushar; Maiti, Sourav; Ghosh, Hirendra N

    2016-04-07

    We have synthesized Mn-doped CdTeSe gradient alloy nanocrystals (NCs) by a colloidal synthetic method, and charge carrier dynamics have been revealed through ultrafast transient absorption (TA) spectroscopy. Due to the reactivity difference between Te and Se, a CdTe-rich core and CdSe-rich shell have been formed in the CdTeSe alloy with the formation of a gradient type II core-shell structure. Electron paramagnetic resonance studies suggest Mn atoms are located in the surface of the alloy NCs. Steady-state optical absorption and emission studies suggest formation of a charge-transfer (CT) state in which electrons are localized in a CdSe-rich shell and holes are localized in a CdTe-rich core which appears in the red region of the spectra. Electron transfer in the CT state is found to take place in the Marcus inverted region. To understand charge-transfer dynamics in the CdTeSe alloy NCs and to determine the effect of Mn doping on the alloy, ultrafast transient absorption studies have been carried out. In the case of the undoped alloy, formation of the CT state is found to take place through electron relaxation to the conduction band of the CT state with a time of 600 fs and through hole relaxation (from the CdSe-rich state to the CdTe-rich state) to the valence band of the CT state with a time scale of 1 ps. However, electron relaxation in the presence of Mn dopants takes place initially via an electron transfer to the Mn 3d state (d(5)) followed by transfer from the Mn 3d state (d(6)) to the CT state, which has been found to take place with a >700 ps time scale in addition to the hole relaxation time of 2 ps. Charge recombination time of the CT state is found to be extremely slow in the Mn-doped CdTeSe alloy NCs as compared to the undoped one, where the Mn atom acts as an electron storage center.

  4. Reactions of the phthalimide N-oxyl radical (PINO) with activated phenols: the contribution of π-stacking interactions to hydrogen atom transfer rates.

    Science.gov (United States)

    D'Alfonso, Claudio; Bietti, Massimo; DiLabio, Gino A; Lanzalunga, Osvaldo; Salamone, Michela

    2013-02-01

    The kinetics of reactions of the phthalimide N-oxyl radical (PINO) with a series of activated phenols (2,2,5,7,8-pentamethylchroman-6-ol (PMC), 2,6-dimethyl- and 2,6-di-tert-butyl-4-substituted phenols) were investigated by laser flash photolysis in CH(3)CN and PhCl in order to establish if the reactions with PINO can provide a useful tool for evaluating the radical scavenging ability of phenolic antioxidants. On the basis of the small values of deuterium kinetic isotope effects, the relatively high and negative ρ values in the Hammett correlations and the results of theoretical calculations, we suggest that these reactions proceed by a hydrogen atom transfer (HAT) mechanism having a significant degree of charge transfer resulting from a π-stacked conformation between PINO and the aromatic ring of the phenols. Kinetic solvent effects were analyzed in detail for the hydrogen transfer from 2,4,6-trimethylphenol to PINO and the data obtained are in accordance with the Snelgrove-Ingold equation for HAT. Experimental rate constants for the reactions of PINO with activated phenols are in accordance with those predicted by applying the Marcus cross relation.

  5. Low-Energy Charge Transfer in Multiply-Charged Ion-Atom Collisions Studied with the Combined SCVB-MOCC Approach

    Directory of Open Access Journals (Sweden)

    B. Zygelman

    2002-03-01

    Full Text Available A survey of theoretical studies of charge transfer involving collisions of multiply-charged ions with atomic neutrals (H and He is presented. The calculations utilized the quantum-mechanical molecular-orbital close-coupling (MOCC approach where the requisite potential curves and coupling matrix elements have been obtained with the spin-coupled valence bond (SCVB method. Comparison is made among various collision partners, for equicharged systems, where it is illustrated that even for total charge transfer cross sections, scaling-laws do not exist for low-energy collisions (i.e. < 1 keV/amu. While various empirical scaling-laws are well known in the intermediateand high-energy regimes, the multi-electron configurations of the projectile ions results in a rich and varied low-energy dependence, requiring an explicit calculation for each collision-partner pair. Future charge transfer problems to be addressed with the combined SCVB-MOCC approach are briefly discussed.

  6. Anti-oxidant activity of 6-gingerol as a hydroxyl radical scavenger by hydrogen atom transfer, radical addition and electron transfer mechanisms

    Indian Academy of Sciences (India)

    MANISH K TIWARI; P C MISHRA

    2016-08-01

    Mechanisms of anti-oxidant action of 6-gingerol as a hydroxyl radical scavenger have been investigated using the transition state theory within the framework of density functional theory. Hydrogen abstraction by a hydroxyl radical from the different sites of 6-gingerol and addition of the former to the different sites ofthe latter were studied. Electron transfer from 6-gingerol to a hydroxyl radical was also studied. Solvent effect in aqueous media was treated using the integral equation formalism of the polarizable continuum model (IEFPCM). Reaction rate constants in aqueous media were generally found to be larger than those in gas phase. The tunneling contributions to rate constants were found to be appreciable. Our results show that 6-gingerol is an excellent anti-oxidant and would scavenge hydroxyl radicals efficiently.

  7. Functionalization of PEDOT by Click Chemistry and ATRP

    DEFF Research Database (Denmark)

    Hoffmann, Christian; Daugaard, Anders Egede

    Poly(3,4‐ethylenedioxythiophene) (PEDOT) is a conductive polymer which has received increasing attention and many developments have been investigated. PEDOT has been applied in many different areas such as biosensors or polymer solar cells. This work presents a modification of PEDOT films through...... Click Chemistry with alkynes followed by activator regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP) to develop PEDOT films with anti‐fouling properties through application of a model system based on a crosslinked surface of polystyrene PS‐N3....

  8. A benchmark test suite for proton transfer energies and its use to test electronic structure model chemistries

    Science.gov (United States)

    Nachimuthu, Santhanamoorthi; Gao, Jiali; Truhlar, Donald G.

    2012-05-01

    We present benchmark calculations of nine selected points on potential energy surfaces describing proton transfer processes in three model systems, H5O2+, CH3OH…H+…OH2, and CH3COOH…OH2. The calculated relative energies of these geometries are compared to those calculated by various wave function and density functional methods, including the polarized molecular orbital (PMO) model recently developed in our research group and other semiempirical molecular orbital methods. We found that the SCC-DFTB and PMO methods (the latter available so far only for molecules consisting of only O and H and therefore only for the first of the three model systems) give results that are, on average, within 2 kcal/mol of the benchmark results. Other semiempirical molecular orbital methods have mean unsigned errors (MUEs) of 3-8 kcal/mol, local density functionals have MUEs in the range 0.7-3.7 kcal/mol, and hybrid density functionals have MUEs of only 0.3-1.0 kcal/mol, with the best density functional performance obtained by hybrid meta-GGAs, especially M06 and PW6B95.

  9. Umbrella sampling of proton transfer in a creatine-water system

    Science.gov (United States)

    Ivchenko, Olga; Bachert, Peter; Imhof, Petra

    2014-04-01

    Proton transfer reactions are among the most common processes in chemistry and biology. Proton transfer between creatine and surrounding solvent water is underlying the chemical exchange saturation transfer used as a contrast in magnetic resonance imaging. The free energy barrier, determined by first-principles umbrella sampling simulations (EaDFT 3 kcal/mol) is in the same order of magnitude as the experimentally obtained activation energy. The underlying mechanism is a first proton transfer from the guanidinium group to the water pool, followed by a second transition where a proton is "transferred back" from the nearest water molecule to the deprotonated nitrogen atom of creatine.

  10. Fundamentals of quantum chemistry

    CERN Document Server

    House, J E

    2004-01-01

    An introduction to the principles of quantum mechanics needed in physical chemistry. Mathematical tools are presented and developed as needed and only basic calculus, chemistry, and physics is assumed. Applications include atomic and molecular structure, spectroscopy, alpha decay, tunneling, and superconductivity. New edition includes sections on perturbation theory, orbital symmetry of diatomic molecules, the Huckel MO method and Woodward/Hoffman rules as well as a new chapter on SCF and Hartree-Fock methods. * This revised text clearly presents basic q

  11. Electromagnetically induced absorption due to transfer of coherence and coherence population oscillation for the Fg = 3 →Fe = 4 transition in 85Rb atoms

    Science.gov (United States)

    Rehman, Hafeez Ur; Mohsin, Muhammad Qureshi; Noh, Heung-Ryoul; Kim, Jin-Tae

    2016-12-01

    Lineshapes for the electromagnetically induced absorption (EIA) of thermal 85Rb atoms in a degenerate two-level system have been investigated using matching (σ∥σ , π∥π) and orthogonal (σ ⊥ σ , π ⊥ π) polarization configurations of coupling and probe beams. EIA signals, which result from coherence population oscillation and transfer of coherence of the excited state, are obtained in detail theoretically and experimentally. The observed EIA linewidths, which are limited due to the decoherence rate between the magnetic sublevels in the ground state from transit-time relaxation, match well with the calculated ones. Decompositions of the absorption signals analyzed with respect to magnetic sublevels of the ground state show that enhanced or decreased absorption signals for each component of magnetic sublevels in the ground state depend on several factors. These factors include the decay rates and transition strengths, which determine the overall absorption spectral profile.

  12. Synthesis of biomimetic poly[2-(methacryloyloxy)ethyl phosphorycholine]-coated magnetite nanoparticles via surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Sui, Jie-He; Cao, Chang-Yan; Cai, Wei

    2011-10-01

    Modification of magnetite nanoparticles with biomimetic poly[2-(methacryloyloxy)ethyl phosphorycholine] (poly(MPC)) via surface-initiated atom transfer radical polymerization (ATRP) was carried out. Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analyses (TGA) and zeta potential studies indicated that well defined poly (MPC) was successfully grafted on the surface of magnetite nanoparticles. X-ray diffraction results showed the structure of magnetite nanoparticles after surface modification was not changed. The poly (MPC)-coated magnetite nanoparticles had a mean transmission electron microscopy (TEM) diameter of 11 +/- 1.5 nm. The resulting nanomaterials were superparamagnetic at room temperature, exhibited good colloidal stability in aqueous media and good responsibility to magnetic field. Such magnetite nanoparticles with biomimetic surface have potential application in prolonging circulation time in vivo.

  13. SYNTHESIS OF BLOCK COPOLYMER FROM 5,6-BENZO-2-METHYLENE-1,3-DIOXEPANE AND METHYL ACRYLATE VIA ATOM TRANSFER RADICAL POLYMERIZATION

    Institute of Scientific and Technical Information of China (English)

    Jin-ying Yuan; Cai-yuan Pan

    2002-01-01

    Poly(methyl acrylate)-b-poly(5,6-benzo-2-methylene-1,3-dioxepane) (PMA-b-PBMDO) was synthesized by twostep atom transfer radical polymerization (ATRP). Firstly, ATRP of methyl acrylate (MA) was realized using ethyl α-bromobutyrate (EBrB) as initiator in the presence of CuBr/2,2'-bipyridine. After isolation, poly(methyl acrylate) with terminal bromine (PMA-Br) was synthesized. Secondly, the resulting PMA-Br was used as a macromolecular initiator in the ATRP of BMDO. The structure of block copolymer was characterized by 1H-NMR spectroscopy. Molecular weight and molecular weight distribution were determined on a gel permeation chromatograph (GPC).

  14. Preparation of Mg(OH)2 hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

    Science.gov (United States)

    Wang, Xiao; Zhang, Yue; Lv, Lihua; Cui, Yongzhu; Wei, Chunyan; Pang, Guibing

    2016-02-01

    Mg(OH)2 flame retardant hybrid pigment is synthesized through simultaneous solution precipitation and adsorption of anionic dyes (C.I. Acid Red 6). The Mg(OH)2 hybrid pigment bearing vinyl groups after surface silane modification is immobilized onto the surface of bromo end-functional cellulose fiber by atom transfer radical polymerization (ATRP). The morphology and structure of Mg(OH)2 pigments and cellulose fibers grafted with modified pigments are characterized. The thermal properties, flammability and color fastness of cellulose fibers grafted with modified pigments are measured. The results reveal that anionic dye molecules are adsorbed onto Mg(OH)2 crystals and affect the formation of lamella-like Mg(OH)2 crystals. The cellulose fiber grafted with modified Mg(OH)2 hybrid pigment absorbs about four times heat more than original cellulose fiber with about 4% immobilization ratio of pigment, which shortens nearly half of afterflame time and afterglow time.

  15. The Complex Core Level Spectra of CeO2: An Analysis in Terms of Atomic and Charge Transfer Effects

    Energy Technology Data Exchange (ETDEWEB)

    Bagus, Paul S; Nelin, Constance J; Ilton, Eugene S; Baron, Martin; Abbott, Heather; Primorac, Elena; Kuhlenbeck, Helmut; Shaikhutdinov, Shamil; Freund, Hans-Joachim

    2010-03-05

    We present a rigorous parameter-free theoretical treatment of the Ce 4s and 5s photoelectron spectra of CeO2. In the currently accepted model the satellite structure in the photoelectron spectra is explained in terms of a mixed valence (Ce 4f0 O 2p6, Ce 4f1 O 2p5, and Ce 4f2 O 2p4) configurations. We show that charge transfer (CT) into Ce 5d as well as configurations involving intra-atomic movement of charge must be considered in addition and compute their contributions to the spectra.

  16. A manganese(V)-oxo π-cation radical complex: influence of one-electron oxidation on oxygen-atom transfer.

    Science.gov (United States)

    Prokop, Katharine A; Neu, Heather M; de Visser, Sam P; Goldberg, David P

    2011-10-12

    One-electron oxidation of Mn(V)-oxo corrolazine 2 affords 2(+), the first example of a Mn(V)(O) π-cation radical porphyrinoid complex, which was characterized by UV-vis, EPR, LDI-MS, and DFT methods. Access to 2 and 2(+) allowed for a direct comparison of their reactivities in oxygen-atom transfer (OAT) reactions. Both complexes are capable of OAT to PPh(3) and RSR substrates, and 2(+) was found to be a more potent oxidant than 2. Analysis of rate constants and activation parameters, together with DFT calculations, points to a concerted OAT mechanism for 2(+) and 2 and indicates that the greater electrophilicity of 2(+) likely plays a dominant role in enhancing its reactivity. These results are relevant to comparisons between Compound I and Compound II in heme enzymes.

  17. Atomic scattering in the diffraction limit: electron transfer in keV Li+-Na(3s, 3p) collisions

    DEFF Research Database (Denmark)

    Poel, Mike van der; Nielsen, C.V.; Rybaltover, M.;

    2002-01-01

    . This setup yields a momentum resolution of 0.12 an, an order of magnitude better angular resolution than previous measurements on this system. This enables us to clearly resolve Fraunhofer-type diffraction patterns in the angle DCS. In particular, the angular width of the ring structure is given by the ratio...... of the de Broglie wavelength lambda(dB) = 150 fm at a velocity v = 0.20 au and the effective atomic diameter for electron capture 2R = 20 au. Parallel AO and MO semiclassical coupled-channel calculations of the Na(3s, 3p) --> Li(2s, 2p) state-to-state collision amplitudes have been performed, and quantum...

  18. Inorganic-organic hybrid coatings on stainless steel by layer-by-layer deposition and surface-initiated atom-transfer-radical polymerization for combating biocorrosion.

    Science.gov (United States)

    Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

    2009-03-01

    To improve the biocorrosion resistance of stainless steel (SS) and to confer the bactericidal function on its surface for inhibiting bacterial adhesion and biofilm formation, well-defined inorganic-organic hybrid coatings, consisting of the inner compact titanium oxide multilayers and outer dense poly(vinyl-N-hexylpyridinium) brushes, were successfully developed. Nanostructured titanium oxide multilayer coatings were first built up on the SS substrates via the layer-by-layer sol-gel deposition process. The trichlorosilane coupling agent, containing the alkyl halide atom-transfer-radical polymerization (ATRP) initiator, was subsequently immobilized on the titanium oxide coatings for surface-initiated ATRP of 4-vinylpyridine (4VP). The pyridium nitrogen moieties of the covalently immobilized 4VP polymer, or P(4VP), brushes were quaternized with hexyl bromide to produce a high concentration of quaternary ammonium salt on the SS surfaces. The excellent antibacterial efficiency of the grafted polycations, poly(vinyl-N-pyridinium bromide), was revealed by viable cell counts and atomic force microscopy images of the surface. The effectiveness of the hybrid coatings in corrosion protection was verified by the Tafel plot and electrochemical impedance spectroscopy measurements.

  19. The tert-butoxyl radical mediated hydrogen atom transfer reactions of the Parkinsonian proneurotoxin 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine and selected tertiary amines.

    Science.gov (United States)

    Suleman, N Kamrudin; Flores, Joey; Tanko, James M; Isin, Emre Mehmet; Castagnoli, Neal

    2008-09-15

    Previous studies have shown that the hydrogen atom transfer (HAT) reactions of tert-butoxyl radical from the Parkinsonian proneurotoxin 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP) occur with low selectivity at the allylic and non-allylic alpha-C-H positions. In this paper, we report a more comprehensive regiochemical study on the reactivity of the tert-butoxyl radical as well as on the associated primary kinetic deuterium isotope effects for the various hydrogen atom abstractions of MPTP. In addition, the results of a computational study to estimate the various C-H bond dissociation energies of MPTP are presented. The results of the present study show the allylic/non-allylic selectivity is approximately 73:21. The behavior of the tert-butoxyl radical mediated oxidation of MPTP contrasts with this reaction as catalyzed by monoamine oxidase B (MAO-B) that occurs selectively at the allylic alpha-carbon. These observations lead to the conclusion that the tert-butoxyl radical is not a good chemical model for the MAO-B-catalyzed bioactivation of MPTP.

  20. From Cathode Rays To Alpha Particles To Quantum of Action: A Rational Reconstruction of Structure of the Atom and Its Implications for Chemistry Textbooks.

    Science.gov (United States)

    Niaz, Mansoor

    1998-01-01

    Reports on a study that involves the analysis of chemistry textbooks at the college freshman level to determine the degree to which they address developments in the history and philosophy of science. Twenty-three textbooks were evaluated on eight criteria. Contains 108 references. (DDR)

  1. Fluorine in medicinal chemistry.

    Science.gov (United States)

    Swallow, Steven

    2015-01-01

    Since its first use in the steroid field in the late 1950s, the use of fluorine in medicinal chemistry has become commonplace, with the small electronegative fluorine atom being a key part of the medicinal chemist's repertoire of substitutions used to modulate all aspects of molecular properties including potency, physical chemistry and pharmacokinetics. This review will highlight the special nature of fluorine, drawing from a survey of marketed fluorinated pharmaceuticals and the medicinal chemistry literature, to illustrate key concepts exploited by medicinal chemists in their attempts to optimize drug molecules. Some of the potential pitfalls in the use of fluorine will also be highlighted.

  2. Intramolecular proton or hydrogen-atom transfer in the ground- and excited-states of 2-hydroxybenzophenone: A theoretical study

    Energy Technology Data Exchange (ETDEWEB)

    Yi, Ping G. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China); Liang, Yong H. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China)], E-mail: kaixgl@sina.com.cn; Cao, Chen Z. [School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan 411201 (China)

    2005-08-29

    The internal rotational motion and the ground- and excited-state intramolecular proton transfer (GISPT, EISPT) reaction of 2-hydroxybenzophenone (HBP) are studied at the B3LYP/6-31G**, CIS/6-31G** and TD B3LYP/6-31++G** level. The calculated results show that there is only one minimum at the S{sub 0} and S{sub 1} state, the enol form (E) is the single minimum at the S{sub 0} state, and its rotamers and tautomers are with more than 8.24 and 10.43 kcal/mol less stable, respectively, however, the keto tautomer (K*) is the single minimum at the S{sub 1} state. Therefore, the ground- and excited-state intramolecular proton transfer reacts without a barrier between E and K or E* and K*. The energy gap between the first excited electronic state S{sub 1} 1({pi}, {pi}*){sup 1} and the second excited electronic state S{sub 2} 2(n, {pi}*){sup 1} of E is only 0.019 eV at CIS/6-31G** level. So the S{sub 0} {yields} S{sub 1} and S{sub 0} {yields} S{sub 2} excitation may occur at the same time, and the S{sub 1} state may occur the EISPT process and result a large Stokes shifted fluorescence. And the S{sub 2} state may through internal conversion to the S{sub 1} state or intersystem crossing to the T{sub 2} state. These theoretical results contrast with the conclusion of Nakayama and his coworkers [M. Hagiri, N. Ichinose, J. Kinugasa, T. Iwasa, T. Nakayama, Chem. Lett. 33 (2004) 326] stating the present of two ground-state conformers of HBP.

  3. Understanding Atomic Structure: Is There a More Direct and Compelling Connection between Atomic Line Spectra and the Quantization of an Atom's Energy?

    Science.gov (United States)

    Rittenhouse, Robert C.

    2015-01-01

    The "atoms first" philosophy, adopted by a growing number of General Chemistry textbook authors, places greater emphasis on atomic structure as a key to a deeper understanding of the field of chemistry. A pivotal concept needed to understand the behavior of atoms is the restriction of an atom's energy to specific allowed values. However,…

  4. Understanding Atomic Structure: Is There a More Direct and Compelling Connection between Atomic Line Spectra and the Quantization of an Atom's Energy?

    Science.gov (United States)

    Rittenhouse, Robert C.

    2015-01-01

    The "atoms first" philosophy, adopted by a growing number of General Chemistry textbook authors, places greater emphasis on atomic structure as a key to a deeper understanding of the field of chemistry. A pivotal concept needed to understand the behavior of atoms is the restriction of an atom's energy to specific allowed values. However,…

  5. A transfer of carbon atoms from fatty acids to sugars and amino acids in yellow lupine (Lupinus luteus L.) seedlings.

    Science.gov (United States)

    Borek, Sławomir; Ratajczak, Wiktoria; Ratajczak, Lech

    2003-05-01

    The metabolism of 14C-acetate was investigated during the in vitro germination of yellow lupine seeds. Carbon atoms (14C) from the C-2 position of acetate were incorporated mainly into amino acids: aspartate, glutamate, and glutamine and into sugars: glucose, sucrose, and fructose. In contrast to this, 14C from the C-1 position of acetate was released mainly as 14CO2. Incorporation of 1-14C and 2-14C from acetate into amino acids and sugars in seedling axes was more intense when sucrose was added to the medium. However, in cotyledons where lipids are converted to carbohydrates, this process was inhibited by exogenous sucrose. Since acetate is the product of fatty acid beta-oxidation, our results indicate that, at least in lupine, seed storage lipids can be converted not only to sucrose, but mainly to amino acids. Inhibitory effects of sucrose on the incorporation of 14C from acetate into amino acids and sugars in cotyledons of lupine seedlings may be explained as the effect of regulation of the glyoxylate cycle by sugars.

  6. Reproducible In-Silico Folding of a Four Helix 60 Amino Acid Protein in a Transferable All-Atom Forcefield

    Science.gov (United States)

    Schug, Alexander

    2005-03-01

    For predicting the protein tertiary structure one approach describes the native state of a protein as the global minimum of an appropiate free-energy forcefield. We have recently developed such a all-atom protein forcefield (PFF01). As major challenge remains the search for the global minimum for which we developed efficient methods. Using these we were able to predict the structure of helical proteins from different families ranging in size from 20 to 60 amino acids starting with random configurations. For the four helix 60 amino acid protein Bacterial Ribosomal Protein L20 (pdb code: 1GYZ) we used a simple client-master model for distributed computing. Starting from a set of random structures three phases of different folding simulations refined this set to a final one with 50 configurations. During this process the amount of native-like structures increased strongly. Six out of the ten structures best in energy approached the native structure within 5 åbackbone rmsd. The conformation with the lowest energy had a backbone rmsd value of 4.6 åtherefore correctly predicting the tertiary structure of 1GYZ.ReferencesA. Schug et al, Phys. Rev. Letters, 91:158102, 2003A. Schug et al, J. Am. Chem. Soc. (in press), 2004

  7. A study of effective atomic number and electron density of gel dosimeters and human tissues for scattering of gamma rays: momentum transfer, energy and scattering angle dependence.

    Science.gov (United States)

    Kurudirek, Murat

    2016-11-01

    The objective of this work was to study water- and tissue-equivalent properties of some gel dosimeters, human tissues and water, for scattering of photons using the effective atomic number (Z eff). The Rayleigh to Compton scattering ratio (R/C) was used to obtain Z eff and electron density (N e ) of gel dosimeters, human tissues and water considering a 10(-2)-10(9) momentum transfer, q (Å(-1)). In the present work, a logarithmic interpolation procedure was used to estimate R/C as well as Z eff of the chosen materials in a wide scattering angle (1°-180°) and energy range (0.001-100 MeV). The Z eff of the chosen materials was found to increase as momentum transfer increases, for q > ~1 Å(-1). At fixed scattering angle and energy, Z eff of the material first increases and then becomes constant for high momentum transfers (q ≥ 3 Å(-1)), which indicates that Z eff is almost independent of energy and scattering angle for the chosen materials. Based on the Z eff data and the continuous momentum transfer range (10(-2)-10(9) Å(-1)), MAGIC, PAGAT and soft tissue were found to be water-equivalent materials, since their differences (%) relative to water are significantly low (≤3.2 % for MAGIC up to 10(3) Å(-1), ≤2.9 % for PAGAT up to 10(9) Å(-1), and ≤3.8 % for soft tissue up to 10(9) Å(-1)), while the Fricke gel was not found to be water equivalent. PAGAT was found to be a soft tissue-equivalent material in the entire momentum transfer range (<4.3 %), while MAGAT has shown to be tissue equivalent for brain (≤8.1 % up to 10 Å(-1)) and lung (<8.2 % up to 10 Å(-1)) tissues. The Fricke gel dosimeter has shown to be adipose tissue equivalent for most of the momentum range considered (<10 %).

  8. Art in Chemistry: Chemistry in Art. Second Edition

    Science.gov (United States)

    Greenberg, Barbara R.; Patterson, Dianne

    2008-01-01

    This textbook integrates chemistry and art with hands-on activities and fascinating demonstrations that enable students to see and understand how the science of chemistry is involved in the creation of art. It investigates such topics as color integrated with electromagnetic radiation, atoms, and ions; paints integrated with classes of matter,…

  9. Art in Chemistry: Chemistry in Art. Second Edition

    Science.gov (United States)

    Greenberg, Barbara R.; Patterson, Dianne

    2008-01-01

    This textbook integrates chemistry and art with hands-on activities and fascinating demonstrations that enable students to see and understand how the science of chemistry is involved in the creation of art. It investigates such topics as color integrated with electromagnetic radiation, atoms, and ions; paints integrated with classes of matter,…

  10. Gas phase ion chemistry

    CERN Document Server

    Bowers, Michael T

    1979-01-01

    Gas Phase Ion Chemistry, Volume 2 covers the advances in gas phase ion chemistry. The book discusses the stabilities of positive ions from equilibrium gas-phase basicity measurements; the experimental methods used to determine molecular electron affinities, specifically photoelectron spectroscopy, photodetachment spectroscopy, charge transfer, and collisional ionization; and the gas-phase acidity scale. The text also describes the basis of the technique of chemical ionization mass spectrometry; the energetics and mechanisms of unimolecular reactions of positive ions; and the photodissociation

  11. Quest for new materials: Inorganic chemistry plays a crucial role

    Indian Academy of Sciences (India)

    J Gopalakrishnan; Rohini Mani

    2009-05-01

    There is an endless quest for new materials to meet the demands of advancing technology. Thus, we need new magnetic and metallic/semiconducting materials for spintronics, new low-loss dielectrics for telecommunication, new multi-ferroic materials that combine both ferroelectricity and ferromagnetism for memory devices, new piezoelectrics that do not contain lead, new lithium containing solids for application as cathode/anode/electrolyte in lithium batteries, hydrogen storage materials for mobile/transport applications and catalyst materials that can convert, for example, methane to higher hydrocarbons, and the list is endless! Fortunately for us, chemistry - inorganic chemistry in particular - plays a crucial role in this quest. Most of the functional materials mentioned above are inorganic non-molecular solids, while much of the conventional inorganic chemistry deals with isolated molecules or molecular solids. Even so, the basic concepts that we learn in inorganic chemistry, for example, acidity/basicity, oxidation/reduction (potentials), crystal field theory, low spin-high spin/inner sphere-outer sphere complexes, role of -electrons in transition metal chemistry, electron-transfer reactions, coordination geometries around metal atoms, Jahn-Teller distortion, metal-metal bonds, cation-anion (metal-nonmetal) redox competition in the stabilization of oxidation states - all find crucial application in the design and synthesis of inorganic solids possessing technologically important properties. An attempt has been made here to illustrate the role of inorganic chemistry in this endeavour, drawing examples from the literature as well as from the research work of my group.

  12. DDEC6: A Method for Computing Even-Tempered Net Atomic Charges in Periodic and Nonperiodic Materials

    CERN Document Server

    Manz, Thomas A

    2015-01-01

    Net atomic charges (NACs) are widely used in all chemical sciences to concisely summarize key information about the partitioning of electrons among atoms in materials. Although widely used, there is currently no atomic population analysis method suitable for being used as a default method in quantum chemistry programs. To address this challenge, we introduce a new atoms-in-materials method with the following nine properties: (1) exactly one electron distribution is assigned to each atom, (2) core electrons are assigned to the correct host atom, (3) NACs are formally independent of the basis set type because they are functionals of the total electron distribution, (4) the assigned atomic electron distributions give an efficiently converging polyatomic multipole expansion, (5) the assigned NACs usually follow Pauling scale electronegativity trends, (6) NACs for a particular element have good transferability among different conformations that are equivalently bonded, (7) the assigned NACs are chemically consiste...

  13. International Journal of Quantum Chemistry. Quantum Chemistry Symposium Number 27: Proceedings of the International Symposium on Atomic, Molecular, and Condensed Matter Theory and Computational Methods Held in St. Augustine, Florida on 13-20 March 1993

    Science.gov (United States)

    1993-03-20

    defining a transition for a certain number of atoms that depends * Permanent address. Proyecto Quinor, Facultad de Ciencias Exactas , Universidad Nacional...Universidade Federal de Uberlandia 205 CPL PRC Depto. de Ciencias Fisicas Bartlesv2le, OK 74004 Campus Santa Monica Uberlandia, MG 38400-902 RICHARD...considering the tip, sample and * On leave from: Escuela de Quimica, Facultad de Ciencias . Universidad Central de Venezuela. Apar- tado 47102, Caracas 1020 A

  14. Matrix-isolation studies on the radiation-induced chemistry in H₂O/CO₂ systems: reactions of oxygen atoms and formation of HOCO radical.

    Science.gov (United States)

    Ryazantsev, Sergey V; Feldman, Vladimir I

    2015-03-19

    The radiation-induced transformations occurring upon X-ray irradiation of solid CO2/H2O/Ng systems (Ng = Ar, Kr, Xe) at 8-10 K and subsequent annealing up to 45 K were studied by Fourier transform infrared spectroscopy. The infrared (IR) spectra of deposited matrices revealed the presence of isolated monomers, dimers, and intermolecular H2O···CO2 complexes. Irradiation resulted in effective decomposition of matrix-isolated carbon dioxide and water yielding CO molecules and OH radicals, respectively. Annealing of the irradiated samples led to formation of O3, HO2, and a number of xenon hydrides of HXeY type (in the case of xenon matrices). The formation of these species was used for monitoring of the postirradiation thermally induced chemical reactions involving O and H atoms generated by radiolysis. It was shown that the radiolysis of CO2 in noble-gas matrices produced high yields of stabilized oxygen atoms. In all cases, the temperatures at which O atoms become mobile and react are lower than those of H atoms. Dynamics and reactivity of oxygen atoms was found to be independent of the precursor nature. In addition, the formation of HOCO radicals was observed in all the noble-gas matrices at remarkably low temperatures. The IR spectra of HOCO and DOCO were first characterized in krypton and xenon matrices. It was concluded that the formation of HOCO was mainly due to the radiation-induced evolution of the weakly bound H2O···CO2 complexes. This result indicates the significance of weak intermolecular interactions in the radiation-induced chemical processes in inert low-temperature media.

  15. The atomic structure and chemistry of Fe-rich steps on antiphase boundaries in Ti-doped Bi0.9Nd0.15FeO3

    Directory of Open Access Journals (Sweden)

    Ian MacLaren

    2014-06-01

    Full Text Available Stepped antiphase boundaries are frequently observed in Ti-doped Bi0.85Nd0.15FeO3, related to the novel planar antiphase boundaries reported recently. The atomic structure and chemistry of these steps are determined by a combination of high angle annular dark field and bright field scanning transmission electron microscopy imaging, together with electron energy loss spectroscopy. The core of these steps is found to consist of 4 edge-sharing FeO6 octahedra. The structure is confirmed by image simulations using a frozen phonon multislice approach. The steps are also found to be negatively charged and, like the planar boundaries studied previously, result in polarisation of the surrounding perovskite matrix.

  16. Strong Inhibition of O-Atom Transfer Reactivity for Mn(IV)(O)(π-Radical-Cation)(Lewis Acid) versus Mn(V)(O) Porphyrinoid Complexes.

    Science.gov (United States)

    Zaragoza, Jan Paulo T; Baglia, Regina A; Siegler, Maxime A; Goldberg, David P

    2015-05-27

    The oxygen atom transfer (OAT) reactivity of two valence tautomers of a Mn(V)(O) porphyrinoid complex was compared. The OAT kinetics of Mn(V)(O)(TBP8Cz) (TBP8Cz = octakis(p-tert-butylphenyl)corrolazinato(3-)) reacting with a series of triarylphosphine (PAr3) substrates were monitored by stopped-flow UV-vis spectroscopy, and revealed second-order rate constants ranging from 16(1) to 1.43(6) × 10(4) M(-1) s(-1). Characterization of the OAT transition state analogues Mn(III)(OPPh3)(TBP8Cz) and Mn(III)(OP(o-tolyl)3)(TBP8Cz) was carried out by single-crystal X-ray diffraction (XRD). A valence tautomer of the closed-shell Mn(V)(O)(TBP8Cz) can be stabilized by the addition of Lewis and Brønsted acids, resulting in the open-shell Mn(IV)(O)(TBP8Cz(•+)):LA (LA = Zn(II), B(C6F5)3, H(+)) complexes. These Mn(IV)(O)(π-radical-cation) derivatives exhibit dramatically inhibited rates of OAT with the PAr3 substrates (k = 8.5(2) × 10(-3) - 8.7 M(-1) s(-1)), contrasting the previously observed rate increase of H-atom transfer (HAT) for Mn(IV)(O)(TBP8Cz(•+)):LA with phenols. A Hammett analysis showed that the OAT reactivity for Mn(IV)(O)(TBP8Cz(•+)):LA is influenced by the Lewis acid strength. Spectral redox titration of Mn(IV)(O)(TBP8Cz(•+)):Zn(II) gives Ered = 0.69 V vs SCE, which is nearly +700 mV above its valence tautomer Mn(V)(O)(TBP8Cz) (Ered = -0.05 V). These data suggest that the two-electron electrophilicity of the Mn(O) valence tautomers dominate OAT reactivity and do not follow the trend in one-electron redox potentials, which appear to dominate HAT reactivity. This study provides new fundamental insights regarding the relative OAT and HAT reactivity of valence tautomers such as M(V)(O)(porph) versus M(IV)(O)(porph(•+)) (M = Mn or Fe) found in heme enzymes.

  17. Annual report of the Osaka Laboratory for Radiation Chemistry Japan Atomic Energy Research Institute, (No. 28). April 1, 1994 - March 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    1995-10-01

    The annual research activities of Osaka Laboratory for Radiation Chemistry, JAERI during the fiscal year of 1994 (April 1, 1994 - March 31, 1995) are described. The research activities were conducted under two research programs: the study on laser-induced organic chemical reactions and the study on basic radiation technology for functional materials. Detailed descriptions of the activities are presented as reviews on the following subjects: laser-induced chemical transformation, laser-induced reaction of polymer surface, microprocessing by radiation-induced polymerization, preparation of fine metal particles by gamma ray irradiation, and electron beam dosimetry. The operation report of the irradiation facilities is also included. (author).

  18. Finding the Most Efficient Technology Transfer Route Using Dijkstra Algorithm to Foster Innovation: The Case of Essential Oil Developments in the Research Center for Chemistry at the Indonesian Institute of Sciences

    Directory of Open Access Journals (Sweden)

    Arief Ameir Rahman Setiawan

    2016-07-01

    Full Text Available Innovation is one of the most critical issues in research institutions which can be performed through certain routes within the technology transfer mechanism. As the demands of research implementation are increasing, a better mechanism should be deployed to foster innovation. This study will investigate the possibilities for technology transfer mechanism improvements by (i identifying a number of steps required for innovation; (ii measuring the efficiency of each step; and (iii exploring the most efficient routes to innovate through the Dijkstra algorithm. Cases of research on essential oils and derivatives in the Research Center for Chemistry (RCC of the Indonesian Institute of Sciences (LIPI will be examined as the working example for the study. As a result of this study, a model containing a recommended sequence for the most efficient steps to innovation can be proposed. Using the proposed model, the efficiency rate of the technology transfer mechanism was increased twice, suggesting the possibility of stimulating innovation performance.

  19. Chemistry-nuclear chemistry division. Progress report, October 1979-September 1980

    Energy Technology Data Exchange (ETDEWEB)

    Ryan, R.R. (comp.)

    1981-05-01

    This report presents the research and development programs pursued by the Chemistry-Nuclear Chemistry Division of the Los Alamos National Laboratory. Topics covered include advanced analytical methods, atmospheric chemistry and transport, biochemistry, biomedical research, element migration and fixation, inorganic chemistry, isotope separation and analysis, atomic and molecular collisions, molecular spectroscopy, muonic x rays, nuclear cosmochemistry, nuclear structure and reactions, radiochemical separations, theoretical chemistry, and unclassified weapons research.

  20. Atmospheric chemistry of trans-CF3CH=CHCl: Kinetics of the gas-phase reactions with Cl atoms, OH radicals, and O3

    DEFF Research Database (Denmark)

    Andersen, Mads Peter Sulbaek; Nilsson, Elna Johanna Kristina; Nielsen, Ole John;

    2008-01-01

    Long path length Fourier transform infrared (FTIR)–smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OH radicals and O3 with trans-3,3,3-trifluoro-1-chloropropene, t-CF3CH CHCl, in 700 Torr total pressure at 295±2K. Values of k(Cl + t-CF3CH CHCl) = (5...

  1. Atmospheric chemistry of 4 : 2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH): Products and mechanism of Cl atom initiated oxidation

    DEFF Research Database (Denmark)

    Hurley, MD; Ball, JC; Wallington, TJ;

    2004-01-01

    Smog chamber/FTIR techniques were used to study the products and mechanism of the Cl atom initiated oxidation of 4:2 fluorotelomer alcohol (CF3(CF2)(3)CH2CH2OH) in 700 Torr of N-2/O-2 diluent at 296 K. CF3(CF2)(3)CH2CHO is the sole primary oxidation product. CF3(CF2)(3)CHO, CF3(CF2)(3)CH2COOH, an...

  2. Atomic layer deposition for semiconductors

    CERN Document Server

    Hwang, Cheol Seong

    2014-01-01

    This edited volume discusses atomic layer deposition (ALD) for all modern semiconductor devices, moving from the basic chemistry of ALD and modeling of ALD processes to sections on ALD for memories, logic devices, and machines.

  3. Surface chemistry of copper metal and copper oxide atomic layer deposition from copper(ii) acetylacetonate: a combined first-principles and reactive molecular dynamics study.

    Science.gov (United States)

    Hu, Xiao; Schuster, Jörg; Schulz, Stefan E; Gessner, Thomas

    2015-10-28

    Atomistic mechanisms for the atomic layer deposition using the Cu(acac)2 (acac = acetylacetonate) precursor are studied using first-principles calculations and reactive molecular dynamics simulations. The results show that Cu(acac)2 chemisorbs on the hollow site of the Cu(110) surface and decomposes easily into a Cu atom and the acac-ligands. A sequential dissociation and reduction of the Cu precursor [Cu(acac)2 → Cu(acac) → Cu] are observed. Further decomposition of the acac-ligand is unfavorable on the Cu surface. Thus additional adsorption of the precursors may be blocked by adsorbed ligands. Molecular hydrogen is found to be nonreactive towards Cu(acac)2 on Cu(110), whereas individual H atoms easily lead to bond breaking in the Cu precursor upon impact, and thus release the surface ligands into the gas-phase. On the other hand, water reacts with Cu(acac)2 on a Cu2O substrate through a ligand-exchange reaction, which produces gaseous H(acac) and surface OH species. Combustion reactions with the main by-products CO2 and H2O are observed during the reaction between Cu(acac)2 and ozone on the CuO surface. The reactivity of different co-reactants toward Cu(acac)2 follows the order H > O3 > H2O.

  4. Fabrication of an SPR Sensor Surface with Antifouling Properties for Highly Sensitive Detection of 2,4,6-Trinitrotoluene Using Surface-Initiated Atom Transfer Polymerization

    Directory of Open Access Journals (Sweden)

    Kiyoshi Toko

    2013-07-01

    Full Text Available In this study, we modified a surface plasmon resonance immunosensor chip with a polymer using surface-initiated atom transfer polymerization (SI-ATRP for the highly sensitive detection of 2,4,6-trinitrotoluene (TNT. To immobilize a TNT analogue on the polymer, mono-2-(methacryloyloxyethylsuccinate (MES, which has a carboxyl group, was used in this study. However, the anti-TNT antibody may adsorb non-specifically on the polymer surface by an electrostatic interaction because MES is negatively charged. Therefore, a mixed monomer with MES and diethylaminoethylmethacrylate (DEAEM, which has a tertiary amino group and is positively charged, was prepared to obtain electroneutrality for suppressing the nonspecific adsorption. The detection of TNT was performed by inhibition assay using the polymer surface. To ensure high sensitivity to TNT, the affinity between the surface and the antibody was optimized by controlling the density of the initiator for ATRP by mixing two types of self-assembled monolayer reagents. As a result, a limit of detection of 5.7 pg/mL (ppt for TNT was achieved using the optimized surface.

  5. Ternary hybrid polymeric nanocomposites through grafting of polystyrene on graphene oxide-TiO{sub 2} by surface initiated atom transfer radical polymerization (SI-ATRP)

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Arvind; Bansal, Ankushi; Behera, Babita; Jain, Suman L.; Ray, Siddharth S., E-mail: ssray@iip.res.in

    2016-04-01

    A ternary hybrid of graphene oxide-titania-polystyrene (GO-TiO{sub 2}-PS) nanocomposite is developed where polystyrene composition is regulated by controlling growth of polymer chains and nanoarchitectonics is discussed. Graphene Oxide-TiO{sub 2} (GO-TiO{sub 2}) nanocomposite is prepared by in-situ hydrothermal method and the surface is anchored with α-bromoisobutyryl bromide to activate GO-TiO{sub 2} as initiator for polymerization. In-situ grafting of polystyrene through surface initiated atom transfer radical polymerization (SI- ATRP) on this Br-functionalized nano-composite initiator yields GO-TiO{sub 2}-PS ternary hybrid. Varying the monomer amount and keeping the concentration of initiator constant, polystyrene chain growth is regulated with narrow poly-dispersivity to achieve desired composition. This composite is well characterized by various analytical techniques like FTIR, XRD, DSC, SEM, TEM, and TGA. - Highlights: • Nanocomposite of ternary hybrid of GO-TiO{sub 2} with polystyrene. • PS is surface grafted on GO-TiO{sub 2}. • Polymer chain lengths are well regulated by SI-ATRP living polymerization. • Thermal stability of this hybrid is relatively high.

  6. Synthesis of well-defined structurally silica-nonlinear polymer core-shell nanoparticles via the surface-initiated atom transfer radical polymerization

    Science.gov (United States)

    Chen, Jiucun; Hu, Min; Zhu, Wendong; Li, Yaping

    2011-05-01

    We report on the synthesis of the well-defined structurally silica-nonlinear polymer core-shell nanoparticles via the surface-initiated atom transfer radical polymerization. At first, 3-(2-bromoisobutyramido)propyl(triethoxy)-silane (the ATRP initiator) was prepared by the reaction of 3-aminopropyltriethoxysilane with 2-bromoisobutyryl bromide. The ATRP initiator was covalently attached onto the nanosilica surface. The subsequent ATRP of HEMA from the initiator-attached SiO 2 surface was carried out in order to afforded functional nanoparticles bearing a hydroxyl moiety at the chain end, SiO 2-g-PHEMA-Br. The esterification reaction of pendent hydroxyl moieties of PHEMA segment with 2-bromoisobutyryl bromide afforded the SiO 2-based multifunctional initiator, SiO 2-g-PHEMA(-Br)-Br, bearing one bromine moiety on each monomer repeating unit within the PHEMA segment. Finally, the synthesis of SiO 2-g-PHEMA(-g-PSt)-b-PSt was accomplished by the ATRP of St monomer using SiO 2-g-PHEMA(-Br)-Br as multifunctional initiator. These organic/inorganic hybrid materials have been extensively characterized by FT-IR, XPS, TG, and TEM.

  7. Synthesis and characterization of TiO{sub 2}/Ag/polymer ternary nanoparticles via surface-initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Park, Jung Tae; Koh, Joo Hwan; Seo, Jin Ah [Department of Chemical and Biomolecular Engineering, Yonsei University, 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Cho, Yong Soo [Department of Materials Science and Engineering, Yonsei University, 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea, Republic of); Kim, Jong Hak, E-mail: jonghak@yonsei.ac.kr [Department of Chemical and Biomolecular Engineering, Yonsei University, 262 Seongsanno, Seodaemun-gu, Seoul 120-749 (Korea, Republic of)

    2011-08-01

    We report on the novel ternary hybrid materials consisting of semiconductor (TiO{sub 2}), metal (Ag) and polymer (poly(oxyethylene methacrylate) (POEM)). First, a hydrophilic polymer, i.e. POEM, was grafted from TiO{sub 2} nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. These TiO{sub 2}-POEM brush nanoparticles were used to template the formation of Ag nanoparticles by introduction of a AgCF{sub 3}SO{sub 3} precursor and a NaBH{sub 4} aqueous solution for reduction process. Successful grafting of polymeric chains from the surface of TiO{sub 2} nanoparticles and the in situ formation of Ag nanoparticles within the polymeric chains were confirmed using transmission electron microscopy (TEM), UV-vis spectroscopy, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). FT-IR spectroscopy also revealed the specific interaction of Ag nanoparticles with the C=O groups of POEM brushes. This study presents a simple route for the in situ synthesis of both metal and polymer confined within the semiconductor, producing ternary hybrid inorganic-organic nanomaterials.

  8. Poly(glycidyl methacrylate) grafted CdSe quantum dots by surface-initiated atom transfer radical polymerization: Novel synthesis, characterization, properties, and cytotoxicity studies

    Energy Technology Data Exchange (ETDEWEB)

    Bach, Long Giang; Islam, Md. Rafiqul [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of); Lee, Doh Chang [Department of Chemical and Biomolecular Engineering, KAIST Institute for the Nanocentury (KINC), Korea Advanced Institute of Science and Technology (KAIST), Daejeon 305-701 (Korea, Republic of); Lim, Kwon Taek, E-mail: ktlim@pknu.ac.kr [Department of Imaging System Engineering, Pukyong National University, Busan 608-737 (Korea, Republic of)

    2013-10-15

    A novel approach for the synthesis of poly(glycidyl methacrylate) grafted CdSe quantum dot (QDs) (PGMA-g-CdSe) was developed. The PGMA-g-CdSe nanohybrids were synthesized by the surface-initiated atom transfer radical polymerization of glycidyl methacrylate from the surface of the strategic initiator, CdSe-BrIB QDs prepared by the interaction of 2-bromoisobutyryl bromide (BrIB) and CdSe-OH QDs. The structure, morphology, and optical property of the PGMA-g-CdSe nanohybrids were analyzed by FT-IR, XPS, TGA, XRD, TEM, and PL. The as-synthesized PGMA-g-CdSe nanohybrids having multi-epoxide groups were employed for the direct coupling of biotin via ring-opening reaction of the epoxide groups to afford the Biotin-f-PGMA-g-CdSe nanobioconjugate. The covalent immobilization of biotin onto PGMA-g-CdSe was confirmed by FT-IR, XPS, and EDX. Biocompatibility and imaging properties of the Biotin-f-PGMA-g-CdSe were investigated by MTT bioassay and PL analysis, respectively. The cell viability study suggested that the biocompatibility was significantly enhanced by the functionalization of CdSe QDs by biotin and PGMA.

  9. Enhanced and selective adsorption of mercury ions on chitosan beads grafted with polyacrylamide via surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Li, Nan; Bai, Renbi; Liu, Changkun

    2005-12-06

    Enhanced and selective removal of mercury ions was achieved with chitosan beads grafted with polyacrylamide (chitosan-g-polyacrylamide) via surface-initiated atom transfer radical polymerization (ATRP). The chitosan-g-polyacrylamide beads were found to have significantly greater adsorption capacities and faster adsorption kinetics for mercury ions than the chitosan beads. At pH 4 and with initial mercury concentrations of 10-200 mg/L, the chitosan-g-polyacrylamide beads can achieve a maximum adsorption capacity of up to 322.6 mg/g (in comparison with 181.8 mg/g for the chitosan beads) and displayed a short adsorption equilibrium time of less than 60 min (compared to more than 15 h for the chitosan beads). Coadsorption experiments with both mercury and lead ions showed that the chitosan-g-polyacrylamide beads had excellent selectivity in the adsorption of mercury ions over lead ions at pH mercury adsorption was due to the many amide groups grafted onto the surfaces of the beads, and the selectivity in mercury adsorption can be attributed to the ability of mercury ions to form covalent bonds with the amide. It was found that adsorbed mercury ions on the chitosan-g-polyacrylamide beads can be effectively desorbed in a perchloric acid solution, and the regenerated beads can be reused almost without any loss of adsorption capacity.

  10. End-Functionalized Poly(N-isopropylacrylamide with d-Glucosamine through Different Initiator from C-1 and C-2 Positions via Atom Transfer Radical Polymerization

    Directory of Open Access Journals (Sweden)

    Guihua Cui

    2016-11-01

    Full Text Available Regioselective modification of d-glucosamine (2-amino-2-deoxy-d-glucopyranose, GA through C-1 and C-2 positions to synthesized thermo-responsive D-Glucosamine-poly(N-iso-propylacrylamide (PNIPAM via atom transfer radical polymerization (ATRP was investigated for the first time. Two different schemes of the synthesis for GA derivatives (GA-PNIPAM (i and (ii with well-defined structures using 3,4,6-tri-o-acetyl-2-deoxy-2-phthalimido-β-d-glucopyranose and 1,3,4,6-tetra-o-acetyl-2-amino-2-deoxy-β-d-glucopyranose intermediates were examined. The GA-PNIPAM (ii had an amino at C-2 position, while there was a hydroxyl in GA-PNIPAM (i at this position. Both the resulting oligomers (i and (ii had a narrow dispersity, and no significant cytotoxic response of copolymers (i and (ii was observed in the cell line over the concentration range from 0.1 μg/mL to 1000 μg/mL at any of the exposure times. In addition, it was discovered that GA-PNIPAM (i and (ii inhibited the proliferation of Human Hepatocellular Carcinoma Cells HepG2 as the concentration and the time changed, and the inhibitory activity of polymer (ii was higher than that of he (i. The results suggest that the GA-PNIPAM polymers show excellent biocompatibility in vitro.

  11. Surface grafting of Eu(3+) doped luminescent hydroxyapatite nanomaterials through metal free light initiated atom transfer radical polymerization for theranostic applications.

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Jiang, Ruming; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-08-01

    We reported a simple and efficient method to prepare the hydrophilic luminescent HAp polymer nanocomposites through the combination of ligand exchange and metal free light initiated surface-initiated atom transfer radical polymerization (SI-ATRP) using 10-phenylphenothiazine (PTH) as organic catalyst and 2-methacryloyloxyethyl phosphorylcholine (MPC) and itaconic acid (IA) as monomers. The biological imaging and drug delivery performance of HAp-poly(MPC-IA) nanorods were examined to evaluate their potential for biomedical applications. Results suggested that hydrophilic HAp-poly(MPC-IA) nanorods can be successfully prepared. More importantly, the HAp-poly(MPC-IA) exhibited excellent water dispersibility, desirable biocompatibility and good performance for biological imaging and controlled drug delivery applications. As compared with other controlled living polymerization reactions, the metal free light initiated SI-ATRP displayed many advantages such as easy for handle, mild reaction conditions, toxicity and fluorescence quenching from metal catalysts. Therefore, we believe that this strategy should be a useful and effective strategy for preparation of HAp nanomaterials for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

  12. Grafting N-Isopropyl Acrylamide) from Poly(vinylidene Fluoride) Mirofiltration, Membranes via Direct Surface-Initiated Atom Transfer Radical Polymerization, and Temperature Sensitivity

    Science.gov (United States)

    Chen, Yiwang; Xiao, Jichun; Zhou, Weihua; Deng, Qilan; Nie, Huarong; Wan, Meixiang; Bai, Fenglian

    Well-defined poly(N-isopropyl acrylamide) (PNIPAAm) brushes on commercial hydrophobic poly(vinylidene fluoride) (PVDF) microfiltration membrane surfaces were prepared, via direct atom transfer radical polymerization (ATRP) with the secondary fluorinated site of PVDF as initiator and water as solvent at 80°C. The effect of solvents on the ATRP was studied in detail. The water as reaction solvent was in favor of surface-initiated ATRP of N-isopropyl acrylamide (NIPAAm) from secondary fluoride of PVDF membranes. The chemical composition and structure of the modified PVDF membrane surfaces were determined by attenuated total reflectance (ATR) Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The surface and cross-section morphology of membranes were studied by scanning electron microscopy (SEM). The pore sizes of the pristine PVDF membrane and the PNIPAAm-grafted PVDF membranes were measured using micro-image analysis and process software. The introduction of the well-defined PNIPAAm on the PVDF membrane gave rise to hydrophilicity. Water contact angles of PVDF membranes reduced after the surface grafting of PNIPAAm. Water fluxes and protein solution permeation experiments revealed that the PNIPAAm-grafted PVDF membranes exhibited temperature-responsive permeability. The unique microstructure of PNIPAAm brushes facilitated hydrophilicity below the lower critical solution temperature.

  13. Self-assemblies of γ-CDs with pentablock copolymers PMA-PPO-PEO-PPO-PMA and endcapping via atom transfer radical polymerization of 2-methacryloyloxyethyl phosphorylcholine

    Directory of Open Access Journals (Sweden)

    Jing Lin

    2015-11-01

    Full Text Available Pentablock copolymers PMA-PPO-PEO-PPO-PMA synthesized via atom transfer radical polymerization (ATRP were self-assembled with varying amounts of γ-CDs to prepare poly(pseudorotaxanes (PPRs. When the concentration of γ-CDs was lower, the central PEO segment served as a shell of the micelles and was preferentially bent to pass through the γ-CD cavity to construct double-chain-stranded tight-fit PPRs characterized by a channel-like crystal structure. With an increase in the amount of γ-CDs added, they began to accommodate the poly(methyl acrylate (PMA segments dissociated from the core of the micelles. When more γ-CDs were threaded and slipped over the segments, the γ-CDs were randomly distributed along the pentablock copolymer chain to generate single-chain-stranded loose-fit PPRs and showed no characteristic channel-like crystal structure. All the self-assembly processes of the pentablock copolymers resulted in the formation of hydrogels. After endcapping via in situ ATRP of 2-methacryloyloxyethyl phosphorylcholine (MPC, these single-chain-stranded loose-fit PPRs were transformed into conformational identical polyrotaxanes (PRs. The structures of the PPRs and PRs were characterized by means of 1H NMR, GPC, 13C CP/MAS NMR, 2D 1H NOESY NMR, FTIR, WXRD, TGA and DSC analyses.

  14. Antibacterial inorganic-organic hybrid coatings on stainless steel via consecutive surface-initiated atom transfer radical polymerization for biocorrosion prevention.

    Science.gov (United States)

    Yuan, S J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

    2010-05-04

    To enhance the corrosion resistance of stainless steel (SS) and to impart its surface with antibacterial functionality for inhibiting biofilm formation and biocorrosion, well-defined inorganic-organic hybrid coatings, consisting of a polysilsesquioxane inner layer and quaternized poly(2-(dimethyamino)ethyl methacrylate) (P(DMAEMA)) outer blocks, were prepared via successive surface-initiated atom transfer radical polymerization (ATRP) of 3-(trimethoxysilyl)propyl methacrylate (TMSPMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA). The cross-linked P(TMASPMA), or polysilsesquioxane, inner layer provided a durable and resistant coating to electrolytes. The pendant tertiary amino groups of the P(DMAEMA) outer block were quaternized with alkyl halide to produce a high concentration of quaternary ammonium groups with biocidal functionality. The so-synthesized inorganic-organic hybrid coatings on the SS substrates exhibited good anticorrosion and antibacterial effects and inhibited biocorrosion induced by sulfate-reducing bacteria (SRB) in seawater media, as revealed by antibacterial assay and electrochemical analyses, and they are potentially useful to steel-based equipment under harsh industrial and marine environments.

  15. Synthesis of poly(poly(ethylene glycol) methacrylate)-polyisobutylene ABA block copolymers by the combination of quasiliving carbocationic and atom transfer radical polymerizations.

    Science.gov (United States)

    Szabó, Ákos; Szarka, Györgyi; Iván, Béla

    2015-01-01

    Systematic investigations are carried out on the synthesis of a series of new, unique ABA-type triblock copolymers consisting of the hydrophobic and chemically inert polyisobutylene (PIB) inner and the hydrophilic comb-shaped poly(poly(ethylene glycol) methacrylate) (PPEGMA) polymacromonomer as an outer block. Telechelic PIB macroinitiators with narrow molecular weight distributions (MWD) are synthesized by quasiliving carbocationic polymerization of isobutylene with a bifunctional initiator followed by quantitative chain end derivatizations. Atom transfer radical polymerization (ATRP) of PEGMAs with various molecular weights is investigated by using these macroinitiators. It is found that CuBr is an inefficient ATRP catalyst, while CuCl leads to high, nearly complete conversions of the PEGMA macromonomers. Gel permeation chromatography (GPC) analyses reveal slow initiation of PEGMA at relatively high PIB/PEGMA ratios or with PEGMAs of higher molecular weights due to steric hindrance between the macroinitiator and macromonomer. The occurrence of slow initiation, and not permanent termination, is proven by highly efficient ATRP of a low-molecular-weight monomer, methyl methacrylate, with the block copolymers as macroinitiators. Successful synthesis of PPEGMA-PIB-PPEGMA ABA block copolymers is obtained by using either low-molecular-weight PEGMA or relatively low macroinitiator/macromonomer ratios. Differential scanning calorimetry (DSC) indicates phase separation and significant suppression of the crystallinity of the pendant poly(ethylene glycol) (PEG) chains in these new block copolymers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  16. Preparation of Mg(OH){sub 2} hybrid pigment by direct precipitation and graft onto cellulose fiber via surface-initiated atom transfer radical polymerization

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiao, E-mail: wangxiao@dlpu.edu.cn [School of Textile and Materials Engineering, Dalian Polytechnic University, Dalian, Liaoning Province (China); Zhang, Yue; Lv, Lihua; Cui, Yongzhu; Wei, Chunyan [School of Textile and Materials Engineering, Dalian Polytechnic University, Dalian, Liaoning Province (China); Pang, Guibing [School of Mechanical Engineering and Automation, Dalian Polytechnic University, Dalian, Liaoning Province (China)

    2016-02-15

    Graphical abstract: - Highlights: • Adsorbed anionic dye molecules are conducive to preferential growth of (0 0 1) plane of Mg(OH){sub 2} crystal for Mg(OH){sub 2} pigments. • Uniform coverage of nanosized Mg(OH){sub 2} pigments on fiber surface is achieved via surface-initiated ATRP. • About 4 wt% of Mg(OH){sub 2} pigment on fiber surface shortens nearly half of burning time of cellulose. - Abstract: Mg(OH){sub 2} flame retardant hybrid pigment is synthesized through simultaneous solution precipitation and adsorption of anionic dyes (C.I. Acid Red 6). The Mg(OH){sub 2} hybrid pigment bearing vinyl groups after surface silane modification is immobilized onto the surface of bromo end-functional cellulose fiber by atom transfer radical polymerization (ATRP). The morphology and structure of Mg(OH){sub 2} pigments and cellulose fibers grafted with modified pigments are characterized. The thermal properties, flammability and color fastness of cellulose fibers grafted with modified pigments are measured. The results reveal that anionic dye molecules are adsorbed onto Mg(OH){sub 2} crystals and affect the formation of lamella-like Mg(OH){sub 2} crystals. The cellulose fiber grafted with modified Mg(OH){sub 2} hybrid pigment absorbs about four times heat more than original cellulose fiber with about 4% immobilization ratio of pigment, which shortens nearly half of afterflame time and afterglow time.

  17. Enhanced Reactivity in Hydrogen Atom Transfer from Tertiary Sites of Cyclohexanes and Decalins via Strain Release: Equatorial C-H Activation vs Axial C-H Deactivation.

    Science.gov (United States)

    Salamone, Michela; Ortega, Vanesa B; Bietti, Massimo

    2015-05-01

    Absolute rate constants for hydrogen atom transfer (HAT) from cycloalkanes and decalins to the cumyloxyl radical (CumO(•)) were measured by laser flash photolysis. Very similar reactivities were observed for the C-H bonds of cyclopentane and cyclohexane, while the tertiary C-H bond of methylcyclopentane was found to be 6 times more reactive than the tertiary axial C-H bond of methylcyclohexane, pointing toward a certain extent of tertiary axial C-H bond deactivation. Comparison between the cis and trans isomers of 1,2-dimethylcyclohexane, 1,4-dimethylcyclohexane and decalin provides a quantitative evaluation of the role played by strain release in these reactions. kH values for HAT from tertiary equatorial C-H bonds were found to be at least 1 order of magnitude higher than those for HAT from the corresponding tertiary axial C-H bonds (kH(eq)/kH(ax) = 10-14). The higher reactivity of tertiary equatorial C-H bonds was explained in terms of 1,3-diaxial strain release in the HAT transition state. Increase in torsional strain in the HAT transition state accounts instead for tertiary axial C-H bond deactivation. The results are compared with those obtained for the corresponding C-H functionalization reactions by dioxiranes and nonheme metal-oxo species indicating that CumO(•) can represent a convenient model for the reactivity patterns of these oxidants.

  18. Hydrogen atom transfer from 1,n-alkanediamines to the cumyloxyl radical. Modulating C-H deactivation through acid-base interactions and solvent effects.

    Science.gov (United States)

    Milan, Michela; Salamone, Michela; Bietti, Massimo

    2014-06-20

    A time-resolved kinetic study on the effect of trifluoroacetic acid (TFA) on the hydrogen atom transfer (HAT) reactions from 1,n-alkanediamines (R2N(CH2)nNR2, R = H, CH3; n = 1-4), piperazine, and 1,4-dimethylpiperazine to the cumyloxyl radical (CumO(•)), has been carried out in MeCN and DMSO. Very strong deactivation of the α-C-H bonds has been observed following nitrogen protonation and the results obtained have been explained in terms of substrate basicity, of the distance between the two basic centers and of the solvent hydrogen bond acceptor ability. At [substrate] ≤ 1/2 [TFA] the substrates exist in the doubly protonated form HR2N(+)(CH2)nN(+)R2H, and no reaction with CumO(•) is observed. At 1/2 [TFA] [TFA], HAT occurs from the α-C-H bonds of R2N(CH2)nNR2, and the mesured kH values are very close to those obtained in the absence of TFA. Comparison between MeCN and DMSO clearly shows that in the monoprotonated diamines R2N(CH2)nN(+)R2H remote C-H deactivation can be modulated through solvent hydrogen bonding.

  19. Kinetic solvent effects on the reactions of the cumyloxyl radical with tertiary amides. Control over the hydrogen atom transfer reactivity and selectivity through solvent polarity and hydrogen bonding.

    Science.gov (United States)

    Salamone, Michela; Mangiacapra, Livia; Bietti, Massimo

    2015-01-16

    A laser flash photolysis study on the role of solvent effects on hydrogen atom transfer (HAT) from the C-H bonds of N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), N-formylpyrrolidine (FPRD), and N-acetylpyrrolidine (APRD) to the cumyloxyl radical (CumO(•)) was carried out. From large to very large increases in the HAT rate constant (kH) were measured on going from MeOH and TFE to isooctane (kH(isooctane)/kH(MeOH) = 5-12; kH(isooctane)/kH(TFE) > 80). This behavior was explained in terms of the increase in the extent of charge separation in the amides determined by polar solvents through solvent-amide dipole-dipole interactions and hydrogen bonding, where the latter interactions appear to play a major role with strong HBD solvents such as TFE. These interactions increase the electron deficiency of the amide C-H bonds, deactivating these bonds toward HAT to an electrophilic radical such as CumO(•), indicating that changes in solvent polarity and hydrogen bonding can provide a convenient method for deactivation of the C-H bond of amides toward HAT. With DMF, a solvent-induced change in HAT selectivity was observed, suggesting that solvent effects can be successfully employed to control the reaction selectivity in HAT-based procedures for the functionalization of C-H bonds.

  20. Grafting of antibacterial polymers on stainless steel via surface-initiated atom transfer radical polymerization for inhibiting biocorrosion by Desulfovibrio desulfuricans.

    Science.gov (United States)

    Yuan, S J; Xu, F J; Pehkonen, S O; Ting, Y P; Neoh, K G; Kang, E T

    2009-06-01

    To enhance the biocorrosion resistance of stainless steel (SS) and to impart its surface with bactericidal function for inhibiting bacterial adhesion and biofilm formation, well-defined functional polymer brushes were grafted via surface-initiated atom transfer radical polymerization (ATRP) from SS substrates. The trichlorosilane coupling agent, containing the alkyl halide ATRP initiator, was first immobilized on the hydroxylated SS (SS-OH) substrates for surface-initiated ATRP of (2-dimethylamino)ethyl methacrylate (DMAEMA). The tertiary amino groups of covalently immobilized DMAEMA polymer or P(DMAEMA), brushes on the SS substrates were quaternized with benzyl halide to produce the biocidal functionality. Alternatively, covalent coupling of viologen moieties to the tertiary amino groups of P(DMAEMA) brushes on the SS surface resulted in an increase in surface concentration of quaternary ammonium groups, accompanied by substantially enhanced antibacterial and anticorrosion capabilities against Desulfovibrio desulfuricans in anaerobic seawater, as revealed by antibacterial assay and electrochemical studies. With the inherent advantages of high corrosion resistance of SS, and the good antibacterial and anticorrosion capabilities of the viologen-quaternized P(DMAEMA) brushes, the functionalized SS is potentially useful in harsh seawater environments and for desalination plants.

  1. Solid H2 versus solid noble-gas environment: Influence on photoinduced hydrogen-atom transfer in matrix-isolated 4(3H)-pyrimidinone

    Science.gov (United States)

    Lapinski, Leszek; Nowak, Maciej J.; Rostkowska, Hanna

    2017-03-01

    UV-induced transformations have been studied for 4(3H)-pyrimidinone monomers isolated in low-temperature Ar, Ne, n-D2, and n-H2 matrices. The observed photochemical behavior of the compound drastically depended on the solid matrix environment. For 4(3H)-pyrimidinone isolated in solid Ar, the UV-induced phototautomeric transformation was clearly the dominating process, leading to a nearly quantitative conversion of the oxo reactant into the hydroxy product. For solid Ne environment, the oxo → hydroxy transformation was still the major photoprocess, but yielding less of the hydroxy product (ca. 64% of the yield in solid Ar). For 4(3H)-pyrimidinone isolated in solid n-H2, the oxo → hydroxy phototautomeric conversion did not occur (or occurred at a very tiny scale). Also for deuterated 4(3D)-pyrimidinone isolated in solid hydrogen, the analogous oxo → deuteroxy phototransformation was not observed. Finally, for the compound trapped in solid n-D2, the oxo → hydroxy phototautomerism clearly occurred, but the yield of the hydroxy tautomer was small (ca. 18% of the yield in solid Ar). Apart from hydrogen-atom-transfer processes, two other phototransformations: generation of open-ring conjugated ketene and valence Dewar isomer were observed for the compound isolated in Ar, Ne, n-D2, and n-H2 matrices.

  2. Preparation of high-capacity, weak anion-exchange membranes by surface-initiated atom transfer radical polymerization of poly(glycidyl methacrylate) and subsequent derivatization with diethylamine

    Science.gov (United States)

    Qian, Xiaolei; Fan, Hua; Wang, Chaozhan; Wei, Yinmao

    2013-04-01

    Ion-exchange membrane is of importance for the development of membrane chromatography. In this work, a high-capacity anion-exchange membrane was prepared by grafting of glycidyl methacrylate (GMA) onto the surface of regenerated cellulose (RC) membranes via surface-initiated atom transfer radical polymerization (SI-ATRP) and subsequent derivatization with diethylamine. Attenuated total reflectance Fourier-transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were used to characterize changes in the chemical functionality, surface topography and pore morphology of the modified membranes. The static capacity of the prepared anion-exchange membrane was evaluated with bovine serum albumin (BSA) as a model protein. The results indicated that the anion-exchange membrane which could reach a maximum capacity of 96 mg/mL for static adsorption possesses a higher adsorption capacity, and the adsorption capacity increases with the polymerization time. The effect of pH and salt concentration confirmed that the adsorption of BSA followed ion-exchange mechanism. The established method would have potential application in the preparation of anion-exchange membrane.

  3. Solid state chemistry an introduction

    CERN Document Server

    Smart, Lesley E

    2012-01-01

    ""Smart and Moore are engaging writers, providing clear explanations for concepts in solid-state chemistry from the atomic/molecular perspective. The fourth edition is a welcome addition to my bookshelves. … What I like most about Solid State Chemistry is that it gives simple clear descriptions for a large number of interesting materials and correspondingly clear explanations of their applications. Solid State Chemistry could be used for a solid state textbook at the third or fourth year undergraduate level, especially for chemistry programs. It is also a useful resource for beginning graduate

  4. COMBINING ATOM TRANSFER RADICAL POLYMERIZATION AND DISULFIDE /THIOL REDOX CHEMISTRY: A ROUTE TO WELL-DEFINED (BIO)DEGRADABLE POLYMERIC MATERIALS. (R829580)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  5. COMBINING ATOM TRANSFER RADICAL POLYMERIZATION AND DISULFIDE /THIOL REDOX CHEMISTRY: A ROUTE TO WELL-DEFINED (BIO)DEGRADABLE POLYMERIC MATERIALS. (R829580)

    Science.gov (United States)

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  6. Atomic and molecular supernovae

    Energy Technology Data Exchange (ETDEWEB)

    Liu, W.

    1997-12-01

    Atomic and molecular physics of supernovae is discussed with an emphasis on the importance of detailed treatments of the critical atomic and molecular processes with the best available atomic and molecular data. The observations of molecules in SN 1987A are interpreted through a combination of spectral and chemical modelings, leading to strong constraints on the mixing and nucleosynthesis of the supernova. The non-equilibrium chemistry is used to argue that carbon dust can form in the oxygen-rich clumps where the efficient molecular cooling makes the nucleation of dust grains possible. For Type Ia supernovae, the analyses of their nebular spectra lead to strong constraints on the supernova explosion models.

  7. Preparation and self-assembly behavior of polystyrene-block-poly (dimethylaminoethyl methacrylate amphiphilic block copolymer using atom transfer radical polymerization

    Directory of Open Access Journals (Sweden)

    2008-03-01

    Full Text Available Asymmetric and semi-symmetric amphiphilic diblock copolymers polystyrene-block-poly (dimethylaminoethyl methacrylate (PS-b-PDMAEMA with the same PS block length of 62 repeat units and quite short (3 repeat units or equivalent (47 repeat units length of PDMAEMA have been prepared simply by varying the ratio of the bromine-terminated macroinitiator polystyrene (PS-Br to DMAEMA using atom transfer radical polymerization (ATRP. The chemical structures and compositions of the PS-b-PDMAEMA block copolymers are studied by nuclear magnetic resonance (NMR spectroscopy, gel permeation chromatography (GPC, and elementary analysis (EA. The self-assembly behaviors of copolymers in N,N-dimethyl formamide (DMF with different pH and dioxane/water binary solvent mixture by direct dissolution method (DD, are studied by transmission electron microscopy (TEM, electron diffracting analysis (EDA, and energy-dispersive analysis of X-rays (EDAX techniques. Transmission electron microscopy results suggest that asymmetric block copolymer PS62-b-PDMAEMA3 (the numbers in the form of footnotes represent repeated units of each monomer in the copolymer can form spherical core-shell micelles, large compound reverse micelles (LCRMs, hexagonal/rhombic phases, reverse hexagonal/rhombic phases, vesicles, reverse vesicles and necklace-like reverse micelles, controlled by common or selective solvent and pH, while most of the aggregates of semi-symmetric PS62-b-PDMAEMA47 are simply spherical, such as spherical core-shell micelles and reverse spherical core-shell micelles, besides hexagonal/rhombic phases. All above structures are controlled by three components of the free energy of aggregation: core-chain stretching, interfacial energy and intercoronal chain interaction.

  8. Preparation of a thick polymer brush layer composed of poly(2-methacryloyloxyethyl phosphorylcholine) by surface-initiated atom transfer radical polymerization and analysis of protein adsorption resistance.

    Science.gov (United States)

    Inoue, Yuuki; Onodera, Yuya; Ishihara, Kazuhiko

    2016-05-01

    The purpose of this study was to prepare a thick polymer brush layer composed of poly(2-methacryloyloxyethyl phosphorylcholine (MPC)) and assess its resistance to protein adsorption from the dissolved state of poly(MPC) chains in an aqueous condition. The thick poly(MPC) brush layer was prepared through the surface-initiated atom transfer radical polymerization (SI-ATRP) of MPC with a free initiator from an initiator-immobilized substrate at given [Monomer]/[Free initiator] ratios. The ellipsometric thickness of the poly(MPC) brush layers could be controlled by the polymerization degree of the poly(MPC) chains. The thickness of the poly(MPC) brush layer in an aqueous medium was larger than that in air, and this tendency became clearer when the polymerization degree of the poly(MPC) increased. The maximum thickness of the poly(MPC) brush layer in an aqueous medium was around 110 nm. The static air contact angle of the poly(MPC) brush layer in water indicated a reasonably hydrophilic nature, which was independent of the thickness of the poly(MPC) brush layer at the surface. This result occurred because the hydrated state of the poly(MPC) chains is not influenced by the environment surrounding them. Finally, as measured with a quartz crystal microbalance, the amount of protein adsorbed from a fetal bovine serum solution (10% in phosphate-buffered saline) on the original substrate was 420 ng/cm(2). However, the poly(MPC) brush layer reduced this value dramatically to less than 50 ng/cm(2). This effect was independent of the thickness of the poly(MPC) brush layer for thicknesses between 20 nm and about 110 nm. These results indicated that the surface covered with a poly(MPC) brush layer is a promising platform to avoid biofouling and could also be applied to analyze the reactions of biological molecules with a high signal/noise ratio.

  9. Surface polyPEGylation of Eu3+ doped luminescent hydroxyapatite nanorods through the combination of ligand exchange and metal free surface initiated atom transfer radical polymerization

    Science.gov (United States)

    Zeng, Guangjian; Liu, Meiying; Heng, Chunning; Huang, Qiang; Mao, Liucheng; Huang, Hongye; Hui, Junfeng; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen

    2017-03-01

    The Eu3+ doped luminescent hydroxyapatite (HAp) nanorods with uniform size and morphology can be synthesized by hydrothermal route. However, these HAp nanorods are coated by hydrophobic oleylamine, which makes them difficult to be dispersed in aqueous solution and impede their biomedical applications. In this work, Eu3+ doped luminescent polymers functionalized HAp nanorods were prepared through the combination of ligand exchange reaction and metal free surface initiated atom transfer radical polymerization (ATRP) method. In this procedure, the amino group functionalized HAp nanorods were first prepared by ligand exchange reaction using adenosine monophosphate (AMP) as ligand. Then the Br-containing initiators (HAp-Br) were introduced onto the surface of HAp-AMP nanorods through the amidation reaction. Finally, polymers functionalized HAp nanorods were prepared by metal free ATRP method using poly(ethylene glycol) methacrylate (PEGMA) as monomer and 10-phenylphenothiazine (PTH) as organic photocatalyst. The properties of these obtained HAp nanocomposites (HAP-polyPEGMA nanorods) were characterized by means of transmission electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy and thermogravimetric analysis in detail. The cell imaging of these HAP-polyPEGMA nanorods was examined using laser scanning confocal microscope to evaluate their biomedical applications. We demonstrated for the first time that hydrophobic luminescent HAp nanorods can be functionalized with polyPEGMA through the combination of ligand exchange reaction and metal free surface initiated ATRP. As compared with the traditional ATRP, the metal free ATRP can overcome the toxic and fluorescence quenching effects of metal catalysts such as copper ions. More importantly, the strategy described in this work should also be utilized for fabrications of many other luminescent polymer nanocomposites due to its good monomer adoptability.

  10. Localized surface plasmon resonance nanosensing of C-reactive protein with poly(2-methacryloyloxyethyl phosphorylcholine)-grafted gold nanoparticles prepared by surface-initiated atom transfer radical polymerization.

    Science.gov (United States)

    Kitayama, Yukiya; Takeuchi, Toshifumi

    2014-06-03

    Highly sensitive and selective protein nanosensing based on localized surface plasmon resonance (LSPR) of gold nanoparticles (AuNPs) on which polymerized specific ligands were grafted as an artificial protein recognition layer for the target protein were demonstrated. As a model, optical nanosensing for C-reactive protein (CRP), a known biomarker for chronic inflammation that predicts the risk of arteriosclerosis or heart attacks, was achieved by measuring the shift of LSPR spectra derived from the change of permittivity of poly(2-methacryloyloxyethyl phosphorylcholine)-grafted AuNPs (PMPC-g-AuNPs) upon interacting with CRP, in which the PMPC-g-AuNPs layer were grafted on AuNPs by surface-initiated atom transfer radical polymerization (ATRP). This nanosensing system was effective even for detecting CRP concentrations in a human serum solution diluted to 1% (w/w), at which point a limit of detection was ~50 ng/mL and nonspecific adsorption of other proteins was negligible. The nanosensing system using specific ligand-grafted AuNPs has several strengths, such as low preparation cost, avoiding the need for expensive instruments, no necessary complex pretreatments, and high stability, because it does not contain biobased molecules. We believe this novel synthetic route for protein nanosensors, composed of AuNPs and a polymerized specific ligand utilizing surface-initiated controlled/living radical polymerization, will provide a foundation for the design and synthesis of nanosensors targeting various other biomarker proteins, paving the way for future advances in the field of biosensing.

  11. 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)

  12. Heterocyclic chemistry

    OpenAIRE

    Hemming, Karl

    2011-01-01

    Recent progress in the synthesis of heterocyclic compounds is presented\\ud 2010 offered highlights in pericyclic chemistry, particularly 1,3-dipolar cycloaddition chemistry, asymmetric synthesis, gold catalysis, organocatalysis, hydroamination, C–H activation and multicomponent reactions.

  13. 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.

  14. Biophysical chemistry.

    Science.gov (United States)

    Häussinger, Daniel; Pfohl, Thomas

    2010-01-01

    Biophysical chemistry at the Department of Chemistry, University of Basel, covers the NMR analysis of protein-protein interaction using paramagnetic tags and sophisticated microscopy techniques investigating the dynamics of biological matter.

  15. Colour Chemistry

    Science.gov (United States)

    Griffiths, J.; Rattee, I. D.

    1973-01-01

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

  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. 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....

  18. Hydrogen-atom transfer in reactions of organic radicals with [Co-II(por)](center dot) (por = porphyrinato) and in subsequent addition of [Co(H)(por)] to olefins

    NARCIS (Netherlands)

    de Bruin, B.; Dzik, W.I.; Li, S.; Wayland, B.B.

    2009-01-01

    The mechanisms for hydrogen-atom transfer from the cyanoisopropyl radical C-center dot(CH3)(2)CN to [Co-II(por)](center dot) (yielding [Co-III(H)(por)] and CH2=C(CH3)(CN); por = porphyrinato) and the insertion of vinyl acetate (CH2=CHOAc) into the Co-H bond of [Co(H)(por)] (giving [Co-III{CH-(OAc)CH

  19. Clarifying Atomic Weights: A 2016 Four-Figure Table of Standard and Conventional Atomic Weights

    Science.gov (United States)

    Coplen, Tyler B.; Meyers, Fabienne; Holden, Norman E.

    2017-01-01

    To indicate that atomic weights of many elements are not constants of nature, in 2009 and 2011 the Commission on Isotopic Abundances and Atomic Weights (CIAAW) of the International Union of Pure and Applied Chemistry (IUPAC) replaced single-value standard atomic weight values with atomic weight intervals for 12 elements (hydrogen, lithium, boron,…

  20. Oxygen atom transfer from {mu}-Oxo-bis[1,4,8,11,15,18,22,25-octakis(trifluoromethyl)ph-thalocya ninato]diiron(III) : evidence for an Fe(IV)=O intermediate.

    Energy Technology Data Exchange (ETDEWEB)

    Chen, M. J.; Rathke, J. W.; Chemical Engineering

    1998-01-01

    The dimeric [(FPc)Fe]2({mu}-O) (1) (FPc is the dianion of 1,4,8,11,15,18,22,25-octakis(trifluoromethyl)phthalocyanine) has been shown to transfer its -oxo atom quantitatively to trimethylphosphine and triphenylphosphine. In the case of triphenylphosphine a base such as 1-methylimidazole (MeIm) or pyridine (py) is needed to induce the oxygen atom transfer. The reaction of 1 with MeIm at -40 C and below gives [(MeIm)(FPc)Fe]2({mu}-O) (4), which disproportionates to give (MeIm)2(FPc)Fe (5) and (FPc)Fe=O (6) at higher temperatures. The oxo atom of 6 has been shown to transfer to triphenylphosphine. Similarly, 6 is generated by the disproportionation of 1 with py. It has also been generated by the oxidation of 1 with t-butyl hydroperoxide. [(FPc)Fe]2({mu}-O) catalyzes the oxidation of hydrocarbons by iodosylbenzene. With stilbenes, styrenes, cyclohexenes and butenes as substrates, both epoxidations and alkyl C-H bond oxidations have been observed. The epoxidation of cis-stilbene leads to a mixture of cis- and trans-stilbene oxides, indicating that epoxidation of cis-stilbene, and possibly other olefins as well, proceeds through a non-concerted mechanism.

  1. Atomic Layer Deposition of Hafnium(IV) Oxide on Graphene Oxide: Probing Interfacial Chemistry and Nucleation by using X-ray Absorption and Photoelectron Spectroscopies.

    Science.gov (United States)

    Alivio, Theodore E G; De Jesus, Luis R; Dennis, Robert V; Jia, Ye; Jaye, Cherno; Fischer, Daniel A; Singisetti, Uttam; Banerjee, Sarbajit

    2015-07-27

    Interfacing graphene with metal oxides is of considerable technological importance for modulating carrier density through electrostatic gating as well as for the design of earth-abundant electrocatalysts. Herein, we probe the early stages of the atomic layer deposition (ALD) of HfO2 on graphene oxide using a combination of C and O K-edge near-edge X-ray absorption fine structure spectroscopies and X-ray photoelectron spectroscopy. Dosing with water is observed to promote defunctionalization of graphene oxide as a result of the reaction between water and hydroxyl/epoxide species, which yields carbonyl groups that further react with migratory epoxide species to release CO2 . The carboxylates formed by the reaction of carbonyl and epoxide species facilitate binding of Hf precursors to graphene oxide surfaces. The ALD process is accompanied by recovery of the π-conjugated framework of graphene. The delineation of binding modes provides a means to rationally assemble 2D heterostructures. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Forensic chemistry.

    Science.gov (United States)

    Bell, Suzanne

    2009-01-01

    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.

  3. Atom, atom-type and total molecular linear indices as a promising approach for bioorganic and medicinal chemistry: theoretical and experimental assessment of a novel method for virtual screening and rational design of new lead anthelmintic.

    Science.gov (United States)

    Marrero-Ponce, Yovani; Castillo-Garit, Juan A; Olazabal, Ervelio; Serrano, Hector S; Morales, Alcidez; Castañedo, Nilo; Ibarra-Velarde, Froylán; Huesca-Guillen, Alma; Sánchez, Alicia M; Torrens, Francisco; Castro, Eduardo A

    2005-02-15

    Helminth infections are a medical problem in the world nowadays. In this paper a novel atom-level chemical descriptor has been applied to estimate the anthelmintic activity. Total and local linear indices and linear discriminant analysis were used to obtain a quantitative model that discriminates between anthelmintic and non-anthelmintic drug-like compounds. The discriminant model has an accuracy of 90.11% in the training set, with a high Matthews' correlation coefficient (MCC=0.80). To assess the robustness and predictive power of the obtained model, internal (leave-n-out) and external validation process was performed. The QSAR model correctly classified 88.55% of compounds in this external prediction set, yielding a MCC of 0.77. Another LDA model was carried out to outline some conclusions about the possible modes of action of anthelmintic drugs. It has an accuracy of 93.50% in the training set, and 80.00% in the external prediction set. After that, the developed model was used in the virtual--in silico--screening and several compounds from the Merck Index, Negwer's Handbook and Goodman and Gilman were identified by the model as anthelmintic. Finally, the experimental assay of an organic chemical (a furylethylene derivative) by an in vivo test permits us to carry out an assessment of the model. An accuracy of 100% with the theoretical predictions was observed. These results suggest that the proposed method will be a good tool for studying the biological properties of drug candidates during the early state of the drug-development process.

  4. Uranium triamidoamine chemistry.

    Science.gov (United States)

    Gardner, Benedict M; Liddle, Stephen T

    2015-07-01

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

  5. The radical trap in atom transfer radical polymerization need not be thermodynamically stable. A study of the MoX(3)(PMe(3))(3) catalysts.

    Science.gov (United States)

    Maria, Sébastien; Stoffelbach, François; Mata, José; Daran, Jean-Claude; Richard, Philippe; Poli, Rinaldo

    2005-04-27

    The molybdenum(III) coordination complexes MoX(3)(PMe(3))(3) (X = Cl, Br, and I) are capable of controlling styrene polymerization under typical atom transfer radical polymerization (ATRP) conditions, in conjunction with 2-bromoethylbenzene (BEB) as an initiator. The process is accelerated by the presence of Al(OPr(i))(3) as a cocatalyst. Electrochemical and synthetic studies aimed at identifying the nature of the spin trap have been carried out. The cyclic voltammogram of MoX(3)(PMe(3))(3) (X = Cl, Br, I) shows partial reversibility (increasing in the order Cl MoX(4)(PMe(3))(3) for X = Cl and Br. On the other hand, I(-) is more easily oxidized than the MoI(3)(PMe(3))(3) complex; thus, the putative MoI(4)(PMe(3))(3) complex is redox unstable. Electrochemical studies of MoI(3)(PMe(3))(3) in the presence of X(-) (X = Cl or Br) reveal the occurrence of facile halide-exchange processes, leading to the conclusion that the MoI(3)X(PMe(3))(3) products are also redox unstable. The oxidation of MoX(3)(PMe(3))(3) with (1)/(2)Br(2) yields MoX(3)Br(PMe(3))(3) (X = Cl, Br), whose molecular nature is confirmed by single-crystal X-ray analyses. On the other hand, the oxidation of MoI(3)(PMe(3))(3) by I(2) slowly yields a tetraiodomolybdate(III) salt of iodotrimethylphosphonium, [Me(3)PI][MoI(4)(PMe(3))(3)], as confirmed by an X-ray study. This product has no controlling ability in radical polymerization. The redox instability of MoI(3)X(PMe(3))(3) can be reconciled with its involvement as a radical trapping species in the MoI(3)(PMe(3))(3)-catalyzed ATRP, given the second-order nature of its decomposition rate.

  6. Electrospun regenerated cellulose nanofibrous membranes surface-grafted with polymer chains/brushes via the atom transfer radical polymerization method for catalase immobilization.

    Science.gov (United States)

    Feng, Quan; Hou, Dayin; Zhao, Yong; Xu, Tao; Menkhaus, Todd J; Fong, Hao

    2014-12-10

    In this study, an electrospun regenerated cellulose (RC) nanofibrous membrane with fiber diameters of ∼200-400 nm was prepared first; subsequently, 2-hydroxyethyl methacrylate (HEMA), 2-dimethylaminoethyl methacrylate (DMAEMA), and acrylic acid (AA) were selected as the monomers for surface grafting of polymer chains/brushes via the atom transfer radical polymerization (ATRP) method. Thereafter, four nanofibrous membranes (i.e., RC, RC-poly(HEMA), RC-poly(DMAEMA), and RC-poly(AA)) were explored as innovative supports for immobilization of an enzyme of bovine liver catalase (CAT). The amount/capacity, activity, stability, and reusability of immobilized catalase were evaluated, and the kinetic parameters (Vmax and Km) for immobilized and free catalase were determined. The results indicated that the respective amounts/capacities of immobilized catalase on RC-poly(HEMA) and RC-poly(DMAEMA) nanofibrous membranes reached 78 ± 3.5 and 67 ± 2.7 mg g(-1), which were considerably higher than the previously reported values. Meanwhile, compared to that of free CAT (i.e., 18 days), the half-life periods of RC-CAT, RC-poly(HEMA)-CAT, RC-poly(DMAEMA)-CAT, and RC-poly(AA)-CAT were 49, 58, 56, and 60 days, respectively, indicating that the storage stability of immobilized catalase was also significantly improved. Furthermore, the immobilized catalase exhibited substantially higher resistance to temperature variation (tested from 5 to 70 °C) and lower degree of sensitivity to pH value (tested from 4.0 and 10.0) than the free catalase. In particular, according to the kinetic parameters of Vmax and Km, the nanofibrous membranes of RC-poly(HEMA) (i.e., 5102 μmol mg(-1) min(-1) and 44.89 mM) and RC-poly(DMAEMA) (i.e., 4651 μmol mg(-1) min(-1) and 46.98 mM) had the most satisfactory biocompatibility with immobilized catalase. It was therefore concluded that the electrospun RC nanofibrous membranes surface-grafted with 3-dimensional nanolayers of polymer chains/brushes would be

  7. High-performance liquid chromatographic method to evaluate the hydrogen atom transfer during reaction between 1,1-diphenyl-2-picryl-hydrazyl radical and antioxidants

    Energy Technology Data Exchange (ETDEWEB)

    Boudier, Ariane; Tournebize, Juliana [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France); Bartosz, Grzegorz [Department of Molecular Biophysics, University of Lodz, Lodz (Poland); El Hani, Safae; Bengueddour, Rachid [Laboratoire de Nutrition et Sante, Biology Department, Faculty of Sciences, Ibn Tofail University, Kenitra (Morocco); Sapin-Minet, Anne [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France); Leroy, Pierre, E-mail: pierre.leroy@pharma.uhp-nancy.fr [CITHEFOR - EA 3452, Faculte de Pharmacie, Nancy-Universite, 5 Rue Albert Lebrun, BP 80403, 54001 Nancy Cedex (France)

    2012-01-20

    Highlights: Black-Right-Pointing-Pointer Both 1,1-diphenyl-2-picrylhydrazyl radical and its product measurement by HPLC. Black-Right-Pointing-Pointer Lowest limit of detection by monitoring 1,1-diphenyl-2-picryl-hydrazine. Black-Right-Pointing-Pointer Adsorption problem of the radical on HPLC parts have been pointed out. - Abstract: 1,1-Diphenyl-2-picrylhydrazyl (DPPH{center_dot}) is a stable nitrogen centred radical widely used to evaluate direct radical scavenging properties of various synthetic or natural antioxidants (AOs). The bleaching rate of DPPH{center_dot} absorbance at 515 nm is usually monitored for this purpose. In order to avoid the interference of complex coloured natural products used as antioxidant supplements or cosmetics, HPLC systems have been reported as alternative techniques to spectrophotometry. They also rely upon measurement of DPPH{center_dot} quenching rate and none of them permits to identify and measure 1,1-diphenyl-2-picryl-hydrazine (DPPH-H), the reduced product of DPPH{center_dot} resulting from hydrogen atom transfer (HAT), which is the main mechanism of the reaction between DPPH{center_dot} and AOs. We presently report an HPLC method devoted to the simultaneous measurement of DPPH{center_dot} and DPPH-H. Both were fully separated on a C18 column eluted with acetonitrile-10 mM ammonium citrate buffer pH 6.8 (70:30, v/v) and detected at 330 nm. Adsorption process of DPPH{center_dot} onto materials of the HPLC system was pointed out. Consequently, the linearity range observed for DPPH{center_dot} was restricted, thus a much lower limit of detection was obtained for DPPH-H than for DPPH{center_dot} using standards (0.02 and 14 {mu}M, respectively). The method was applied to three commonly used AOs, i.e. Trolox{sup Registered-Sign }, ascorbic acid and GSH, and compared with spectrophotometry. Further application to complex matrices (cell culture media, vegetal extracts) and nanomaterials demonstrated (i) its usefulness because of

  8. Metalloporphyrin-mediated asymmetric nitrogen-atom transfer to hydrocarbons: aziridination of alkenes and amidation of saturated C-H bonds catalyzed by chiral ruthenium and manganese porphyrins.

    Science.gov (United States)

    Liang, Jiang-Lin; Huang, Jie-Sheng; Yu, Xiao-Qi; Zhu, Nianyong; Che, Chi-Ming

    2002-04-02

    Chiral metalloporphyrins [Mn(Por*)(OH)(MeOH)] (1) and [Ru(Por*)(CO)(EtOH)] (2) catalyze asymmetric aziridination of aromatic alkenes and asymmetric amidation of benzylic hydrocarbons to give moderate enantiomeric excesses. The mass balance in these nitrogen-atom-transfer processes has been examined. With PhI=NTs as the nitrogen source, the aziridination of styrenes, trans-stilbene, 2-vinylnaphthalene, indene, and 2,2-dimethylchromene catalyzed by complex 1 or 2 resulted in up to 99 % substrate conversions and up to 94 % aziridine selectivities, whereas the amidation of ethylbenzenes, indan, tetralin, 1-, and 2-ethylnaphthalene catalyzed by complex 2 led to substrate conversions of up to 32 % and amide selectivities of up to 91 %. Complex 1 or 2 can also catalyze the asymmetric amidation of 4-methoxyethylbenzene, tetralin, and 2-ethylnaphthalene with "PhI(OAc)(2) + NH(2)SO(2)Me", affording the N-substituted methanesulfonamides in up to 56 % ee with substrate conversions of up to 34 % and amide selectivities of up to 92 %. Extension of the "complex 1 + PhI=NTs" or "complex 1 + PhI(OAc)(2) + NH(2)R (R=Ts, Ns)" amidation protocol to a steroid resulted in diastereoselective amidation of cholesteryl acetate at the allylic C-H bonds at C-7 with substrate conversions of up to 49 % and amide selectivities of up to 90 % (alpha:beta ratio: up to 4.2:1). An aziridination- and amidation-active chiral bis(tosylimido)ruthenium(VI) porphyrin, [Ru(Por*)(NTs)(2)] (3), and a ruthenium porphyrin aziridine adduct, [Ru(Por*)(CO)(TsAz)] (4, TsAz=N-tosyl-2- (4-chlorophenyl)aziridine), have been isolated from the reaction of 2 with PhI=NTs and N-tosyl-2-(4-chlorophenyl)aziridine, respectively. The imidoruthenium porphyrin 3 could be an active species in the aziridination or amidation catalyzed by complex 2 described above. The second-order rate constants for the reactions of 3 with styrenes, 2-vinylnaphthalene, indene, ethylbenzenes, and 2-ethylnaphthalene range from 3.7-42.5x10(-3) dm(3

  9. Recent Advances in Cyanamide Chemistry: Synthesis and Applications.

    Science.gov (United States)

    Prabhath, M R Ranga; Williams, Luke; Bhat, Shreesha V; Sharma, Pallavi

    2017-04-12

    The application of alkyl and aryl substituted cyanamides in synthetic chemistry has diversified multi-fold in recent years. In this review, we discuss recent advances (since 2012) in the chemistry of cyanamides and detail their application in cycloaddition chemistry, aminocyanation reactions, as well as electrophilic cyanide-transfer agents and their unique radical and coordination chemistry.

  10. Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

    Science.gov (United States)

    Heshmat, Mojgan; Privalov, Timofei

    2017-07-06

    By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C6 F5 )3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H2 splitting at the carbonyl carbon atom of (C6 F5 )3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C6 F5 )3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C6 F5 )3 B, as a catalyst, namely, 1) the step of H2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C6 F5 )3 B-ketone adducts in which (C6 F5 )3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C6 F5 )3 B-alkoxide intermediate giving the (C6 F5 )3 B-alcohol adduct, and 3) the SN 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Atmospheric chemistry of isoflurane, desflurane, and sevoflurane: kinetics and mechanisms of reactions with chlorine atoms and OH radicals and global warming potentials.

    Science.gov (United States)

    Sulbaek Andersen, Mads P; Nielsen, Ole J; Karpichev, Boris; Wallington, Timothy J; Sander, Stanley P

    2012-06-21

    The smog chamber/Fourier-transform infrared spectroscopy (FTIR) technique was used to measure the rate coefficients k(Cl + CF(3)CHClOCHF(2), isoflurane) = (4.5 ± 0.8) × 10(-15), k(Cl + CF(3)CHFOCHF(2), desflurane) = (1.0 ± 0.3) × 10(-15), k(Cl + (CF(3))(2)CHOCH(2)F, sevoflurane) = (1.1 ± 0.1) × 10(-13), and k(OH + (CF(3))(2)CHOCH(2)F) = (3.5 ± 0.7) × 10(-14) cm(3) molecule(-1) in 700 Torr of N(2)/air diluent at 295 ± 2 K. An upper limit of 6 × 10(-17) cm(3) molecule(-1) was established for k(Cl + (CF(3))(2)CHOC(O)F). The laser photolysis/laser-induced fluorescence (LP/LIF) technique was employed to determine hydroxyl radical rate coefficients as a function of temperature (241-298 K): k(OH + CF(3)CHFOCHF(2)) = (7.05 ± 1.80) × 10(-13) exp[-(1551 ± 72)/T] cm(3) molecule(-1); k(296 ± 1 K) = (3.73 ± 0.08) × 10(-15) cm(3) molecule(-1), and k(OH + (CF(3))(2)CHOCH(2)F) = (9.98 ± 3.24) × 10(-13) exp[-(969 ± 82)/T] cm(3) molecule(-1); k(298 ± 1 K) = (3.94 ± 0.30) × 10(-14) cm(3) molecule(-1). The rate coefficient of k(OH + CF(3)CHClOCHF(2), 296 ± 1 K) = (1.45 ± 0.16) × 10(-14) cm(3) molecule(-1) was also determined. Chlorine atoms react with CF(3)CHFOCHF(2) via H-abstraction to give CF(3)CFOCHF(2) and CF(3)CHFOCF(2) radicals in yields of approximately 83% and 17%. The major atmospheric fate of the CF(3)C(O)FOCHF(2) alkoxy radical is decomposition via elimination of CF(3) to give FC(O)OCHF(2) and is unaffected by the method used to generate the CF(3)C(O)FOCHF(2) radicals. CF(3)CHFOCF(2) radicals add O(2) and are converted by subsequent reactions into CF(3)CHFOCF(2)O alkoxy radicals, which decompose to give COF(2) and CF(3)CHFO radicals. In 700 Torr of air 82% of CF(3)CHFO radicals undergo C-C scission to yield HC(O)F and CF(3) radicals with the remaining 18% reacting with O(2) to give CF(3)C(O)F. Atmospheric oxidation of (CF(3))(2)CHOCH(2)F gives (CF(3))(2)CHOC(O)F in a molar yield of 93 ± 6% with CF(3)C(O)CF(3) and HCOF as minor products. The IR

  12. Organic chemistry

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2003-08-15

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

  13. Computational chemistry

    OpenAIRE

    2000-01-01

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

  14. 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...

  15. Collisional energy transfer in gaseous xenon with vacuum ultraviolet laser excitation of the 5d[1/2]1 atomic level

    Science.gov (United States)

    Museur, L.; Kanaev, A. V.; Zheng, W. Q.; Castex, M. C.

    1994-12-01

    Time-resolved analysis of the luminescence decay of gaseous xenon has been carried out with one-photon excitation of the 5d[1/2]1 atomic level for the first time. The one-photon selective excitation is realized with a coherent vacuum ultraviolet (VUV) light source generated via nonlinear processes in mercury vapor. Dominant three-body recombination of Xe(5d[1/2]1) atoms with a rate constant of 3.2(0.3)×10-31 cm6 s-1 has been found. Resonance radiation from this atomic level undergoes a self-trapping, which results in its dominant fluorescence decay in the IR with t=4.9(0.7) μs. Branching into two relaxation channels is found at low xenon pressure (5-100 mbar)—both avoiding the 6s[3/2]1 first resonance atomic level and terminating by VUV emission. At higher pressure, the relaxation kinetics changes displaying after 500 mbar the well known effect of ``atomic reservoir'' and radiation from the A1u/0-u molecular state with lifetime of 101(4) ns. The scheme of energy relaxation involving the 5d[1/2]1 atomic level is discussed.

  16. PMMA-Etching-Free Transfer of Wafer-scale Chemical Vapor Deposition Two-dimensional Atomic Crystal by a Water Soluble Polyvinyl Alcohol Polymer Method

    Science.gov (United States)

    van Ngoc, Huynh; Qian, Yongteng; Han, Suk Kil; Kang, Dae Joon

    2016-09-01

    We have explored a facile technique to transfer large area 2-Dimensional (2D) materials grown by chemical vapor deposition method onto various substrates by adding a water-soluble Polyvinyl Alcohol (PVA) layer between the polymethyl-methacrylate (PMMA) and the 2D material film. This technique not only allows the effective transfer to an arbitrary target substrate with a high degree of freedom, but also avoids PMMA etching thereby maintaining the high quality of the transferred 2D materials with minimum contamination. We applied this method to transfer various 2D materials grown on different rigid substrates of general interest, such as graphene on copper foil, h-BN on platinum and MoS2 on SiO2/Si. This facile transfer technique has great potential for future research towards the application of 2D materials in high performance optical, mechanical and electronic devices.

  17. Gas-Phase Covalent And Non-Covalent Ion/ion Chemistry Of Biological Macromolecules

    OpenAIRE

    Stutzman, John Robert

    2013-01-01

    Gas-phase ion/ion chemistry involves the interaction of oppositely charged ions inside of the mass spectrometer. During this gas-phase chemistry, particle transfer (i.e., proton and electron) or synthesis can occur at rapid reaction rates. Particle transfer represents a mature area of ion/ion chemistry, while selective covalent modification represents a fairly new area of gas-phase chemistry. Gas-phase covalent chemistry is based on traditional solution phase organic chemistry. The work de...

  18. Transferases in Polymer Chemistry

    Science.gov (United States)

    van der Vlist, Jeroen; Loos, Katja

    Transferases are enzymes that catalyze reactions in which a group is transferred from one compound to another. This makes these enzymes ideal catalysts for polymerization reactions. In nature, transferases are responsible for the synthesis of many important natural macromolecules. In synthetic polymer chemistry, various transferases are used to synthesize polymers in vitro. This chapter reviews some of these approaches, such as the enzymatic polymerization of polyesters, polysaccharides, and polyisoprene.

  19. 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…

  20. Nuclear Chemistry, Science (Experimental): 5316.62.

    Science.gov (United States)

    Williams, Russell R.

    This nuclear chemistry module includes topics on atomic structure, instability of the nucleus, detection strengths and the uses of radioactive particles. Laboratory work stresses proper use of equipment and safe handling of radioactive materials. Students with a strong mathematics background may consider this course as advanced work in chemistry.…